Methods of hydraulically fracturing and recovering hydrocarbons

ABSTRACT

There is provided synthetic proppants, and in particular polysilocarb derived ceramic proppants. There is further provided hydraulic fracturing treatments utilizing these proppants, and methods of enhance hydrocarbon recovery.

This application: (i) claims under 35 U.S.C. §119(e)(1) the benefit ofthe filing date of Jul. 4, 2013 of U.S. provisional application Ser. No.61/843,014; (ii) claims under 35 U.S.C. §119(e)(1) the benefit of thefiling date of Feb. 28, 2014 of U.S. provisional application Ser. No.61/946,598; and, (iii) is a continuation-in-part of U.S. patentapplication Ser. No. 14/268,150 filed May 2, 2014, which claims, under35 U.S.C. §119(e)(1), the benefit of the filing date of May 2, 2013 ofU.S. provisional application Ser. No. 61/818,906 and the benefit of thefiling date of May 3, 2013 of U.S. provisional application Ser. No.61/818,981 the entire disclosures of each of which are incorporatedherein by reference.

BACKGROUND OF THE INVENTION

Field of the Invention

The present inventions relate to synthetic proppants, ceramic proppantsand polymeric derived ceramic proppants; methods for making theseproppants; fracing fluids utilizing these proppants; and hydraulicfracturing methods with these proppants. In particular, the presentinventions relate to proppants and hydraulic fracturing activities thatutilize polymeric derived siloxane based ceramics. Thus, the presentinventions further relate to treating wells, e.g., hydrocarbon producingwells, water wells and geothermal wells, to increase and enhance theproduction from these wells by siloxane based polymeric derived ceramicproppant hydraulic fracturing. Still more particularly, methods areprovided for increasing the fluid conductivity between a subterraneanformation containing a desired natural resource, e.g., natural gas,crude oil, water, and geothermal heat source, and a well or borehole totransport the natural resource to the surface or a desired location orcollection point for that natural resource.

In the production of natural resources from formations within the eartha well or borehole is drilled into the earth to the location where thenatural resource is believed to be located. These natural resources maybe a hydrocarbon reservoir, containing natural gas, crude oil andcombinations of these; the natural resource may be fresh water; it maybe a heat source for geothermal energy; or it may be some other naturalresource that is located within the ground.

These resource-containing formations may be a few hundred feet, a fewthousand feet, or tens of thousands of feet below the surface of theearth, including under the floor of a body of water, e.g., below the seafloor. In addition to being at various depths within the earth, theseformations may cover areas of differing sizes, shapes and volumes.

Unfortunately, and generally, when a well is drilled into theseformations the natural resources rarely flow into the well at rates,durations and amounts that are economically viable. This problem occursfor several reasons, some of which are well understood, others of whichare not as well understood, and some of which may not yet be known.These problems can relate to the viscosity of the natural resource, theporosity of the formation, the geology of the formation, the formationpressures, and the perforations that place the production tubing in thewell in fluid communication with the formation, to name a few.

Typically, and by way of general illustration, in drilling a well aninitial borehole is made into the earth, e.g., the surface of land orseabed, and then subsequent and smaller diameter boreholes are drilledto extend the overall depth of the borehole. In this manner as theoverall borehole gets deeper its diameter becomes smaller; resulting inwhat can be envisioned as a telescoping assembly of holes with thelargest diameter hole being at the top of the borehole closest to thesurface of the earth.

Thus, by way of example, the starting phases of a subsea drill processmay be explained in general as follows. Once the drilling rig ispositioned on the surface of the water over the area where drilling isto take place, an initial borehole is made by drilling a 36″ hole in theearth to a depth of about 200-300 ft. below the seafloor. A 30″ casingis inserted into this initial borehole. This 30″ casing may also becalled a conductor. The 30″ conductor may or may not be cemented intoplace. During this drilling operation a riser is generally not used andthe cuttings from the borehole, e.g., the earth and other materialremoved from the borehole by the drilling activity are returned to theseafloor. Next, a 26″ diameter borehole is drilled within the 30″casing, extending the depth of the borehole to about 1,000-1,500 ft.This drilling operation may also be conducted without using a riser. A20″ casing is then inserted into the 30″ conductor and 26″ borehole.This 20″ casing is cemented into place. The 20″ casing has a wellheadsecured to it. (In other operations an additional smaller diameterborehole may be drilled, and a smaller diameter casing inserted intothat borehole with the wellhead being secured to that smaller diametercasing.) A BOP (blow out preventer) is then secured to a riser andlowered by the riser to the sea floor; where the BOP is secured to thewellhead. From this point forward all drilling activity in the boreholetakes place through the riser and the BOP.

For a land based drill process, the steps are similar, although thelarge diameter tubulars, 30″-20″ are typically not used. Thus, andgenerally, there is a surface casing that is typically about 13⅜″diameter. This may extend from the surface, e.g., wellhead and BOP, todepths of tens of feet to hundreds of feet. One of the purposes of thesurface casing is to meet environmental concerns in protecting groundwater. The surface casing should have sufficiently large diameter toallow the drill string, product equipment such as ESPs and circulationmud to pass through. Below the casing one or more different diameterintermediate casings may be used. (It is understood that sections of aborehole may not be cased, which sections are referred to as open hole.)These can have diameters in the range of about 9″ to about 7″, althoughlarger and smaller sizes may be used, and can extend to depths ofthousands and tens of thousands of feet. Inside of the casing andextending from a pay zone, or production zone of the borehole up to andthrough the wellhead on the surface is the production tubing. There maybe a single production tubing or multiple production tubings in a singleborehole, with each of the production tubing endings being at differentdepths.

Typically, when completing a well, it is necessary to perform aperforation operation, and perform a hydraulic fracturing, or fracingoperation. In general, when a well has been drilled and casing, e.g., ametal pipe, is run to the prescribed depth, the casing is typicallycemented in place by pumping cement down and into the annular spacebetween the casing and the earth. (It is understood that many differentdown hole casing, open hole, and completion approaches may be used.) Thecasing, among other things, prevents the hole from collapsing and fluidsfrom flowing between permeable zones in the annulus. Thus, this casingforms a structural support for the well and a barrier to the earth.

While important for the structural integrity of the well, the casing andcement present a problem when they are in the production zone. Thus, inaddition to holding back the earth, they also prevent the hydrocarbonsfrom flowing into the well and from being recovered. Additionally, theformation itself may have been damaged by the drilling process, e.g., bythe pressure from the drilling mud, and this damaged area of theformation may form an additional barrier to the flow of hydrocarbonsinto the well. Similarly, in most situations where casing is not neededin the production area, e.g., open hole, the formation itself isgenerally tight, and more typically can be very tight, and thus, willnot permit the hydrocarbons to flow into the well. In some situationsthe formation pressure is large enough that the hydrocarbons readilyflow into the well in an uncased, or open hole. Nevertheless, asformation pressure lessens a point will be reached where the formationitself shuts-off, or significantly reduces, the flow of hydrocarbonsinto the well. Also such low formation pressure could have insufficientforce to flow fluid from the bottom of the borehole to the surface,requiring the use of artificial lift.

To address, in part, this problem of the flow of hydrocarbons (as wellas other resources, e.g., geothermal) into the well being blocked by thecasing, cement and the formation itself, openings, e.g., perforations,are made in the well in the area of the pay zone. Generally, aperforation is a small, about ¼ ″ to about 1″ or 2″ in diameter holethat extends through the casing, cement and damaged formation and goesinto the formation. This hole creates a passage for the hydrocarbons toflow from the formation into the well. In a typical well, a large numberof these holes are made through the casing and into the formation in thepay zone.

Generally, in a perforating operation a perforating tool or gun islowered into the borehole to the location where the production zone orpay zone is located. The perforating gun is a long, typically roundtool, that has a small enough diameter to fit into the casing or tubularand reach the area within the borehole where the production zone isbelieved to be. Once positioned in the production zone a series ofexplosive charges, e.g., shaped charges, are ignited. The hot gases andmolten metal from the explosion cut a hole, i.e., the perf orperforation, through the casing and into the formation. Theseexplosive-made perforations extend a few inches, e.g., 6″ to 18″ intothe formation.

The ability of, or ease with which, the natural resource can flow out ofthe formation and into the well or production tubing (into and out of,for example, in the case of engineered geothermal wells, and someadvanced recovery methods for hydrocarbon wells) can generally beunderstood as the fluid communication between the well and theformation. As this fluid communication is increased several enhancementsor benefits may be obtained: the volume or rate of flow (e.g., gallonsper minute) can increase; the distance within the formation out from thewell where the natural resources will flow into the well can be increase(e.g., the volume and area of the formation that can be drained by asingle well is increased, and it will thus take less total wells torecover the resources from an entire field); the time period when thewell is producing resources can be lengthened; the flow rate can bemaintained at a higher rate for a longer period of time; andcombinations of these and other efficiencies and benefits.

Fluid communication between the formation and the well can be greatlyincreased by the use of hydraulic fracturing techniques. The first usesof hydraulic fracturing date back to the late 1940s and early 1950s. Ingeneral hydraulic fracturing treatments involve forcing fluids down thewell and into the formation, where the fluids enter the formation andcrack, e.g., force the layers of rock to break apart or fracture. Thesefractures create channels or flow paths that may have cross sections ofa few micron's, to a few millimeters, to several millimeters in size,and potentially larger. The fractures may also extend out from the wellin all directions for a few feet, several feet and tens of feet orfurther. It should be remembered that the longitudinal axis of the wellin the reservoir may not be vertical: it may be on an angle (eitherslopping up or down) or it may be horizontal. For example, in therecovery of shale gas and oil the wells are typically essentiallyhorizontal in the reservoir. The section of the well located within thereservoir, i.e., the section of the formation containing the naturalresources, can be called the pay zone.

Typical fluid volumes in a propped fracturing treatment of a formationin general can range from a few thousand to a few million gallons.Proppant volumes can approach several thousand cubic feet. In generalthe objective of a proppant fracturing is to create and enhance fluidcommunication between the wellbore and the hydrocarbons in theformation, e.g., the reservoir. Thus, proppant fracturing techniques areused to create and enhance conductive pathways for the hydrocarbons toget from the reservoir to the wellbore. Further, a desirable way ofenhancing the efficacy of proppant fracturing techniques is to haveuniform proppant distribution. In this manner a uniformly conductivefracture along the wellbore height and fracture half-length can beprovided. However, the complicated nature of proppant settling, and inparticular in non-Newtonian fluids often causes a higher concentrationof proppant to settle down in the lower part of the fracture. This inturn can create a lack of adequate proppant coverage on the upperportion of the fracture and the wellbore. Clustering of proppant,encapsulation, bridging, crushing and embedment are a few negativeoccurrences or phenomena that can lower the potential conductivity ofthe proppant pack, and efficacy of hydraulic fracture and the well.

The fluids used to perform hydraulic fracture can range from verysimple, e.g., water, to very complex. Additionally, these fluids, e.g.,fracing fluids or fracturing fluids, typically carry with themproppants; but not in all cases, e.g., when acids are used to fracturecarbonate formations. Proppants are small particles, e.g., grains ofsand, aluminum shot, sintered bauxite, ceramic beads, resin coated sandor ceramics, that are flowed into the fractures and hold, e.g., “prop”or hold open the fractures when the pressure of the fracturing fluid isreduced and the fluid is removed to allow the resource, e.g.,hydrocarbons, to flow into the well.

In this manner the proppants hold open the fractures, keeping thechannels open so that the hydrocarbons can more readily flow into thewell. Additionally, the fractures greatly increase the surface area fromwhich the hydrocarbons can flow into the well. Proppants may not beneeded, or generally may not be used when acids are used to create afrac and subsequent channel in a carbonate rich reservoir, where theacids dissolve part or all of the rock leaving an opening for theformation fluids to flow to the wellbore.

Typically fracturing fluids consist primarily of water but also haveother materials in them. The number of other materials, e.g., chemicaladditives used in a typical fracture treatment varies depending on theconditions of the specific well being fractured. Generally, a typicalfracture treatment will use from about 2 to about 25 additives.

Generally the predominant fluids being used for fracture treatments inthe shale formations are water-based fracturing fluids mixed withfriction-reducing additives, e.g., slick water, or slick water fracs.Overall the concentration of additives in most slick water fracturingfluids is generally about 0.5% to 2% with water and sand making up 98%to 99.5% by weight. The addition of friction reducers allows fracturingfluids and proppant to be pumped to the target zone at a higher rate andreduced pressure than if water alone were used.

In addition to friction reducers, other such additives may be, forexample, biocides to prevent microorganism growth and to reducebiofouling of the fractures; oxygen scavengers and other stabilizers toprevent corrosion of metal pipes; and acids that are used to removedrilling mud damage within the near-wellbore.

Further these chemicals and additives could be one or more of thefollowing, and may have the following uses or address the followingneeds: diluted acid (15%), e.g., hydrochloric acid or muriatic acid,which may help dissolve minerals and initiate cracks in the rock; abiocide, e.g., glutaraldehyde, which eliminates bacteria in the waterthat produce corrosive byproducts; a breaker, e.g., ammonium persulfate,which allows a delayed break down of the gel polymer chains; a corrosioninhibitor, e.g., N,N-dimethyl formamide, which prevents the corrosion ofpipes and equipment; a cross-linker, e.g., borate salts, which maintainsfluid viscosity as temperature increases; a friction reducer; e.g.,polyacrylamide or mineral oil, which minimizes friction between thefluid and the pipe; guar gum or hydroxyethyl cellulose, which thickensthe water in order to help suspend the proppant; an iron control agent,e.g., citric acid, which prevents precipitation of metal oxides;potassium chloride, which creates a brine carrier fluid; an oxygenscavenger, e.g., ammonium bisulfite, which removes oxygen from the waterto reduce corrosion; a pH adjuster or buffering agent, e.g., sodium orpotassium carbonate, which helps to maintain the effectiveness of otheradditives, such as, e.g., the cross-linker; scale inhibitor, e.g.,ethylene glycol, which prevents scale deposits in pipes and equipment;and a surfactant, e.g., isopropanol, which is used to increase theviscosity of the fracture fluid.

The composition of the fluid, the characteristics of the proppant, theamount of proppant, the pressures and volumes of fluids used, the numberof times, e.g., stages, when the fluid is forced into the formation, andcombinations and variations of these and other factors may bepreselected and predetermined for specific fracturing jobs, based uponthe formation, geology, perforation type, nature and characteristics ofthe natural resource, and formation pressure, among other things.

Generally, proppant transport inside a hydraulic fracture has twocomponents when the fracture is being generated. The horizontalcomponent is generally dictated by the fluid velocity and associatedstreamlines which help carry proppant to the tip of the fracture. Thevertical component is generally dictated by the terminal particlesettling velocity of the proppant particle in the fluid and is afunction of proppant diameter and density as well as fluid viscosity anddensity. The terminal settling velocity, the fluid velocity, and thusthe proppant transportation and deposit into the fractures can befurther effected and complicated by the various phenomena and conditionspresent during the fracturing operation.

Proppant characteristics can play an important, if not critical role, inthe success of the hydraulic fracturing operation. The proppants'ability to remain dispersed in the fluid and flow to the desiredlocations in the fractures, and to do so in a predictable manner to formpacks, or assemblies of proppant in manners that enhance, rather thanrestrict, the flow of the natural resource being recovered is based uponits characteristics. The proppants must also be cost effective andpreferably inexpensive to make and use, because of the large amounts ofproppant material that is required for a fracturing job. Yet they mustbe strong enough to withstand the pressures of the formation and keepthe fractures open. They must also be compatible with the various othercomponents of the fracturing fluid, which for example, may includeacids, such as HCl. Thus, for these and other reasons, the art hassearched for, but prior to the present inventions has failed to find, alow density, highly uniform, inexpensive, and strong proppant.

Materials made of, or derived from, carbosilane or polycarbosilane(Si—C), silane or polysilane (Si—Si), silazane or polysilazane(Si—N—Si), silicon carbide (SiC), carbosilazane or polycarbosilazane(Si—N—Si—C—Si), siloxane or polysiloxanes (Si—O) are known. Thesegeneral types of materials have great, but unrealized promise; and havefailed to find large-scale applications or market acceptance. Instead,their use has been relegated to very narrow, limited, low volume, highpriced and highly specific applications, such as a ceramic component ina rocket nozzle, or a patch for the space shuttle. Thus, they havefailed to obtain wide spread use as ceramics, and it is believed theyhave obtained even less acceptance and use, if any, as a plasticmaterial, e.g., cured but not pyrolized.

To a greater or lesser extent all of these materials and the processused to make them suffer from one or more failings, including forexample: they are exceptionally expensive and difficult to make, havingcosts in the thousands and tens-of-thousands of dollars per pound; theyrequire high and very high purity starting materials; the processrequires hazardous organic solvents such as toluene, tetrahydrofuran(THF), and hexane; the materials are incapable of making non-reinforcedstructures having any usable strength; the process produces undesirableand hazardous byproducts, such as hydrochloric acid and sludge, whichmay contain magnesium; the process requires multiple solvent and reagentbased reaction steps coupled with curing and pyrolizing steps; thematerials are incapable of forming a useful prepreg; and their overallphysical properties are mixed, e.g., good temperature properties buthighly brittle.

As a result, although believed to have great promise, these types ofmaterials have failed to find large-scale applications or marketacceptance and have remained essentially scientific curiosities.

Related Art and Terminology

As used herein, unless specified otherwise, the terms “hydrocarbonexploration and production”, “exploration and production activities”,“E&P”, and “E&P activities”, and similar such terms are to be giventheir broadest possible meaning, and include surveying, geologicalanalysis, well planning, reservoir planning, reservoir management,drilling a well, workover and completion activities, hydrocarbonproduction, flowing of hydrocarbons from a well, collection ofhydrocarbons, secondary and tertiary recovery from a well, themanagement of flowing hydrocarbons from a well, and any other upstreamactivities.

As used herein, unless specified otherwise, the term “earth” should begiven its broadest possible meaning, and includes, the ground, allnatural materials, such as rocks, and artificial materials, such asconcrete, that are or may be found in the ground.

As used herein, unless specified otherwise “offshore” and “offshoredrilling activities” and similar such terms are used in their broadestsense and would include drilling activities on, or in, any body ofwater, whether fresh or salt water, whether manmade or naturallyoccurring, such as for example rivers, lakes, canals, inland seas,oceans, seas, such as the North Sea, bays and gulfs, such as the Gulf ofMexico. As used herein, unless specified otherwise the term “offshoredrilling rig” is to be given its broadest possible meaning and wouldinclude fixed towers, tenders, platforms, barges, jack-ups, floatingplatforms, drill ships, dynamically positioned drill ships,semi-submersibles and dynamically positioned semi-submersibles. As usedherein, unless specified otherwise the term “seafloor” is to be givenits broadest possible meaning and would include any surface of the earththat lies under, or is at the bottom of, any body of water, whetherfresh or salt water, whether manmade or naturally occurring.

As used herein, unless specified otherwise, the term “borehole” shouldbe given it broadest possible meaning and includes any opening that iscreated in the earth that is substantially longer than it is wide, suchas a well, a well bore, a well hole, a micro hole, a slimhole and otherterms commonly used or known in the arts to define these types of narrowlong passages. Wells would further include exploratory, production,abandoned, reentered, reworked, and injection wells. They would includeboth cased and uncased wells, and sections of those wells. Uncasedwells, or section of wells, also are called open holes, or open holesections. Boreholes may further have segments or sections that havedifferent orientations, they may have straight sections and arcuatesections and combinations thereof. Thus, as used herein unless expresslyprovided otherwise, the “bottom” of a borehole, the “bottom surface” ofthe borehole and similar terms refer to the end of the borehole, i.e.,that portion of the borehole furthest along the path of the boreholefrom the borehole's opening, the surface of the earth, or the borehole'sbeginning. The terms “side” and “wall” of a borehole should to be giventheir broadest possible meaning and include the longitudinal surfaces ofthe borehole, whether or not casing or a liner is present, as such,these terms would include the sides of an open borehole or the sides ofthe casing that has been positioned within a borehole. Boreholes may bemade up of a single passage, multiple passages, connected passages,(e.g., branched configuration, fishboned configuration, or combconfiguration), and combinations and variations thereof.

As used herein, unless specified otherwise, the term “advancing aborehole”, “drilling a well”, and similar such terms should be giventheir broadest possible meaning and include increasing the length of theborehole. Thus, by advancing a borehole, provided the orientation is nothorizontal and is downward, e.g., less than 90°, the depth of theborehole may also be increased.

Boreholes are generally formed and advanced by using mechanical drillingequipment having a rotating drilling tool, e.g., a bit. For example, andin general, when creating a borehole in the earth, a drilling bit isextending to and into the earth and rotated to create a hole in theearth. To perform the drilling operation the bit must be forced againstthe material to be removed with a sufficient force to exceed the shearstrength, compressive strength or combinations thereof, of thatmaterial. The material that is cut from the earth is generally known ascuttings, e.g., waste, which may be chips of rock, dust, rock fibers andother types of materials and structures that may be created by the bit'sinteractions with the earth. These cuttings are typically removed fromthe borehole by the use of fluids, which fluids can be liquids, foams orgases, or other materials know to the art.

The true vertical depth (“TVD”) of a borehole is the distance from thetop or surface of the borehole to the depth at which the bottom of theborehole is located, measured along a straight vertical line. Themeasured depth (“MD”) of a borehole is the distance as measured alongthe actual path of the borehole from the top or surface to the bottom.As used herein unless specified otherwise the term depth of a boreholewill refer to MD. In general, a point of reference may be used for thetop of the borehole, such as the rotary table, drill floor, well head orinitial opening or surface of the structure in which the borehole isplaced.

As used herein, unless specified otherwise, the term “drill pipe” is tobe given its broadest possible meaning and includes all forms of pipeused for drilling activities; and refers to a single section or piece ofpipe. As used herein the terms “stand of drill pipe,” “drill pipestand,” “stand of pipe,” “stand” and similar type terms should be giventheir broadest possible meaning and include two, three or four sectionsof drill pipe that have been connected, e.g., joined together, typicallyby joints having threaded connections. As used herein the terms “drillstring,” “string,” “string of drill pipe,” string of pipe” and similartype terms should be given their broadest definition and would include astand or stands joined together for the purpose of being employed in aborehole. Thus, a drill string could include many stands and manyhundreds of sections of drill pipe.

As used herein, unless specified otherwise, the terms “workover,”“completion” and “workover and completion” and similar such terms shouldbe given their broadest possible meanings and would include activitiesthat take place at or near the completion of drilling a well, activitiesthat take place at or the near the commencement of production from thewell, activities that take place on the well when the well is aproducing or operating well, activities that take place to reopen orreenter an abandoned or plugged well or branch of a well, and would alsoinclude for example, perforating, cementing, acidizing, fracturing,pressure testing, the removal of well debris, removal of plugs,insertion or replacement of production tubing, forming windows in casingto drill or complete lateral or branch wellbores, cutting and millingoperations in general, insertion of screens, stimulating, cleaning,testing, analyzing and other such activities.

As used herein, unless specified otherwise, the terms “formation,”“reservoir,” “pay zone,” and similar terms, are to be given theirbroadest possible meanings and would include all locations, areas, andgeological features within the earth that contain, may contain, or arebelieved to contain, hydrocarbons.

As used herein, unless specified otherwise, the terms “field,” “oilfield” and similar terms, are to be given their broadest possiblemeanings, and would include any area of land, sea floor, or water thatis loosely or directly associated with a formation, and moreparticularly with a resource containing formation, thus, a field mayhave one or more exploratory and producing wells associated with it, afield may have one or more governmental body or private resource leasesassociated with it, and one or more field(s) may be directly associatedwith a resource containing formation.

As used herein, unless specified otherwise, the terms “conventionalgas”, “conventional oil”, “conventional”, “conventional production” andsimilar such terms are to be given their broadest possible meaning andinclude hydrocarbons, e.g., gas and oil, that are trapped in structuresin the earth. Generally, in these conventional formations thehydrocarbons have migrated in permeable, or semi-permeable formations toa trap, or area where they are accumulated. Typically, in conventionalformations a non-porous layer is above, or encompassing the area ofaccumulated hydrocarbons, in essence trapping the hydrocarbonaccumulation. Conventional reservoirs have been historically the sourcesof the vast majority of hydrocarbons produced. As used herein, unlessspecified otherwise, the terms “unconventional gas”, “unconventionaloil”, “unconventional”, “unconventional production” and similar suchterms are to be given their broadest possible meaning and includeshydrocarbons that are held in impermeable rock, and which have notmigrated to traps or areas of accumulation.

As used herein, unless stated otherwise, room temperature is 25° C. And,standard temperature and pressure is 25° C. and 1 atmosphere. As usedherein, unless stated otherwise, generally, the term “about” is meant toencompass a variance or range of ±10%, the experimental or instrumenterror associated with obtaining the stated value, and preferably thelarger of these.

SUMMARY

There has been a long-standing, expanding and unmeet need, for improvedways to obtain resources, and in particular, hydrocarbon resources fromthe earth. Hydraulic fracturing technology, and in particular proppantsand fracturing fluids, have not advanced at a sufficient rate and pace,to keep up with the evolution and advances in hydrocarbon explorationand production. Thus, there exists a long felt, increasing andunfulfilled need for, among other things, a proppant material havingpredetermined characteristics to enhance hydraulic fracturing operationsand the recovery of natural resources, such as oil and natural gas, fromwells. The present inventions, among other things, solve these needs byproviding the articles of manufacture, devices and processes taught, anddisclosed herein.

Thus, there is provided a method of enhancing conductivity of a well toincrease the recovery of hydrocarbons from a subterranean hydrocarbonreservoir associated with the well, the method including: positioning apolysiloxane derived ceramic proppant in a fluid channel in asubterranean reservoir comprising hydrocarbons, whereby the proppant isin fluid association with the hydrocarbons; and, flowing thehydrocarbons over the polysiloxane derived ceramic proppant; and,recovering the hydrocarbons that have flowed over the proppant.

Further there are provided methods and proppants that may have one ormore of the following features: the proppant is a material resultingfrom the pyrolysis of a polymeric precursor comprising a backbone havingthe formula —R₁—Si—C—C—Si—O—Si—C—C—Si—R₂—, where R₁ and R₂ comprisematerials selected from the group consisting of methyl, hydroxyl, vinyland allyl; the proppant is a filled proppant; the proppant is apolysilocarb derived ceramic proppant; the proppant is made up ofsilicon, carbon and oxygen; wherein the proppant is made from apolysilocarb batch comprising a precursor selected from the groupconsisting of methyl hydrogen, siloxane backbone additive, vinylsubstituted and vinyl terminated polydimethyl siloxane, vinylsubstituted and hydrogen terminated polydimethyl siloxane, allylterminated polydimethyl siloxane, silanol terminated polydimethylsiloxane, hydrogen terminated polydimethyl siloxane, vinyl terminateddiphenyl dimethyl polysiloxane, hydroxyl terminated diphenyl dimethylpolysiloxane, hydride terminated diphenyl dimethyl polysiloxane, styrenevinyl benzene dimethyl polysiloxane, andtetramethyltetravinylcyclotetrasiloxane; wherein the proppant is madefrom a polysilocarb batch comprising a precursor comprising methylhydrogen and a siloxane backbone additive; wherein the proppant is madefrom a polysilocarb batch comprising a precursor comprising styrenevinyl benzene dimethyl polysiloxane; wherein the proppant is made from apolysilocarb batch comprising a precursor comprising methyl hydrogen,vinyl terminated polydimethyl siloxane, andtetramethyltetravinylcyclotetrasiloxane; wherein the proppant is madefrom a polysilocarb batch comprising a precursor comprising methylhydrogen, vinyl terminated polydimethyl siloxane,tetramethyltetravinylcyclotetrasiloxane and a catalyst; wherein theproppant is made from a polysilocarb batch comprising a precursorcomprising a methyl terminated hydride substituted polysiloxane; whereinthe proppant is made from a polysilocarb batch comprising a precursorselected from the group consisting of a methyl terminated vinylpolysiloxane, a vinyl terminated vinyl polysiloxane, a hydrideterminated vinyl polysiloxane, and an allyl terminated dimethylpolysiloxane; wherein the proppant is made from a polysilocarb batchcomprising a precursor selected from the group consisting of a vinylterminated dimethyl polysiloxane, a hydroxy terminated dimethylpolysiloxane, a hydride terminated dimethyl polysiloxane, and a hydroxyterminated vinyl polysiloxane; and, wherein the proppant is made from apolysilocarb batch comprising a precursor selected from the groupconsisting of a phenyl terminated dimethyl polysiloxane, a phenyl andmethyl terminated dimethyl polysiloxane, a methyl terminated dimethyldiphenyl polysiloxane, a vinyl terminated dimethyl diphenylpolysiloxane, a hydroxy terminated dimethyl diphenyl polysiloxane, and ahydride terminated dimethyl diphenyl polysiloxane.

Yet further there are provided proppants that can consists essentiallyof silicon, carbon and oxygen, e.g., its main and primary materials are,silicon, carbon and oxygen, while other minor, non-functional componentsmay be present. Additionally, there provided proppants that can consistof silicon, carbon and oxygen, e.g., they are made up solely of silicon,carbon, and oxygen.

In addition there are provided methods and proppants that may have oneor more of the following features: wherein the proppant is made from apolysilocarb batch comprising a molar ratio of hydride groups to vinylgroups is about 1.12 to 1 to about 2.36 to 1; wherein the proppant ismade from a polysilocarb batch comprising a molar ratio of hydridegroups to vinyl groups is about 1.50 to 1; wherein the proppant is madefrom a polysilocarb batch comprising a molar ratio of hydride groups tovinyl groups is about 3.93 to 1; wherein the proppant is made from apolysilocarb batch comprising a molar ratio of hydride groups to vinylgroups is about 5.93 to 1; wherein the proppant is a spherical proppant;wherein the proppant is an essentially perfectly spherical proppant;and, wherein the proppant a substantially perfectly spherical proppant.

Further there are provided methods and proppants that may have one ormore of the following features: wherein the hydrocarbon is natural gasand the formation is a shale formation; wherein the hydrocarbon is crudeoil and the formation is a shale formation; wherein the shale formationis Barnett shale; wherein the shale formation is Bakken shale; whereinthe shale formation is Utica shale; and wherein the shale formation isEagleford shale; and wherein the shale formation is another shaleformation known or later discovered.

Moreover, there is provided a method of enhancing conductivity of a wellto increase the recovery of hydrocarbons from a subterranean hydrocarbonreservoir associated with the well, the method including: positioning asynthetic proppant in a fluid channel in a subterranean reservoircomprising hydrocarbons, whereby the proppant is in fluid associationwith the hydrocarbons; the proppant having an apparent specific gravityof less than about 2 and a crush test of less than about 1% finesgenerated at 10,000 psi., flowing the hydrocarbons over the polysiloxanederived ceramic proppant; and, recovering the hydrocarbons that haveflowed over the proppant.

Yet still further there are provided methods and proppants that may haveone or more of the following features: wherein the proppant has anactual density and an apparent density; and the actual density andapparent density are within 5% of each other; wherein the proppant hasan actual density and an apparent density; and the actual density andapparent density are the same; wherein the proppant has a specificgravity of less than, a crush test of less than about 1% fines generatedat 15,000 psi; wherein the plurality of proppants has at least about100,000 spherical type proppants; and wherein the plurality of proppantshas at least about 1,000,000 spherical type proppants.

Further there is provided a method of enhancing conductivity of a wellto increase the recovery of hydrocarbons from a subterranean hydrocarbonreservoir associated with the well, the method including: positioning asynthetic proppant in a fluid channel in a subterranean reservoircomprising hydrocarbons, whereby the proppant is in fluid associationwith the hydrocarbons; the proppant having an apparent specific gravityof less than about 2.5 and a crush test of less than about 1% finesgenerated at 15,000 psi., flowing the hydrocarbons over the polysiloxanederived ceramic proppant; and, recovering the hydrocarbons that haveflowed over the proppant.

Furthermore, there is provided a method of enhancing conductivity of awell to increase the recovery of hydrocarbons from a subterraneanhydrocarbon reservoir associated with the well, including: positioning aceramic proppant in a fluid channel in a subterranean reservoircomprising hydrocarbons, whereby the proppant is in fluid associationwith the hydrocarbons; the proppant comprises silicon, oxygen andcarbon; and, flowing the hydrocarbons over the proppant; and, recoveringthe hydrocarbons that have flowed over the proppant.

Yet still further there are provided methods and proppants that may haveone or more of the following features: wherein the proppant has aspecific gravity of less than 2; wherein the proppant has a crush testof less than about 1% fines generated at 15,000 psi; and, wherein theproppant has a specific gravity of less than 2, a crush test of lessthan about 1% fines generated at 15,000 psi.

In addition there is provided a method of hydraulically fracturing awell, including: preparing at least about 100,000 gallons of a hydraulicfracturing fluid, the hydraulic fracturing fluid comprising apolysiloxane derived ceramic proppant; pumping at least about 100,000gallons of hydraulic fracturing fluid into a borehole in a formation,and out of the borehole into the formation; whereby fractures arecreated in the formation; and, leaving at least some of the proppant inthe fractures.

Yet still further there are provided methods and proppants that may haveone or more of the following features: wherein the fracturing fluid hasat least about 1 lb per gallon of proppant; wherein the fracturing fluidhas at least about 2 lbs per gallon of proppant; the fracturing fluidhas at least 3 lbs per gallon of proppant; wherein the fracturing fluidhas at least 4 lbs per gallon of proppant; the fracturing fluid has atleast 5 lbs per gallon of proppant, at least about 8 lbs/gal; at leastabout 10 lbs/gal; and about 12 lbs/gal or more.

Still further there is provided a method of hydraulically fracturing awell, the method including: preparing at least about 100,000 gallons ofa hydraulic fracturing fluid, the hydraulic fracturing fluid comprisinga synthetic proppant; the proppant having an apparent specific gravityof less than about 2 and a crush test of less than about 1% finesgenerated at 10,000 psi., pumping at least about 100,000 gallons ofhydraulic fracturing fluid into a borehole in a formation, and out ofthe borehole into the formation; whereby fractures are created in theformation; and, leaving at least some of the proppant in the fractures.

Moreover, there is provided a method of hydraulically fracturing a well,including: preparing at least about 100,000 gallons of a hydraulicfracturing fluid, the hydraulic fracturing fluid comprising a syntheticproppant; the proppant having an apparent specific gravity of less thanabout 2.5 and a crush test of less than about 1% fines generated at15,000 psi., pumping at least about 100,000 gallons of hydraulicfracturing fluid into a borehole in a formation, and out of the boreholeinto the formation; whereby fractures are created in the formation; and,leaving at least some of the proppant in the fractures.

Still additionally there is provide a method of enhancing conductivityof a well to increase the recovery of hydrocarbons from a subterraneanhydrocarbon reservoir associated with the well, the method including:locating a plurality of polysiloxane derived ceramic proppants in flowchannels in a subterranean formation comprising a reservoir ofhydrocarbons, whereby the proppants are in contact with the formationand the hydrocarbons; and, a well connecting a surface of the earth tothe formation; moving the hydrocarbons from the formation through theproppant containing flow channels and into the well; and moving thehydrocarbons to the surface.

Yet still further there are provided methods and proppants that may haveone or more of the following features: wherein the proppants have aparticle size disruption of at least about 95% of the proppants beingwithin about a 10 mesh range; wherein the proppants have a specificgravity of less 1.9; wherein the proppants have a bulk density of lessabout 1.3 g/cc; wherein the proppants have a bulk density of less about1.3 g/cc.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a Scanning Electron Photomicrograph (SEM) of an embodiment ofa spherical polysiloxane derived ceramic (“PsDC”) proppant in accordancewith the present invention (440×, 300 μm reference bar).

FIG. 2 is an SEM of an embodiment of a PsDC in accordance with thepresent invention after being subjected to a load, and exposing internalsurfaces in accordance with the present inventions (370×, 360 μmreference bar).

FIG. 3 is a Krumbein and Sloss Sphericity and Roundness chart.

FIG. 4 is a chart comparing the conductivity data for an embodiment ofproppants in accordance with the present invention with publishedconductivity data for prior art proppants.

FIG. 5 is a table and chart showing increased propped area for anembodiment of a PsDC hydraulic fracture treatment in accordance with thepresent invention.

FIG. 6 is a perspective view of a formation showing increased proppedarea and geometry for an embodiment of a PsDC hydraulic fracture inaccordance with the present invention.

FIG. 7 is a chart showing the increase in initial production (“IP) andan increase in decline curve reduction (“DCR”) for an embodiment of aPsDC hydraulic fracture treatment in accordance with the presentinvention.

FIG. 8 is a perspective view of a hydraulic fracturing site inaccordance with the present inventions.

FIG. 9 is a schematic diagram and flow chart for an embodiment of aprocess for making embodiments of PsDC proppants in accordance with thepresent inventions.

FIG. 10 is a chemical formula for an embodiment of a methyl terminatedhydride substituted polysiloxane precursor material in accordance withthe present inventions.

FIG. 11 is a chemical formula for an embodiment of a methyl terminatedvinyl polysiloxane precursor material in accordance with the presentinventions.

FIG. 12 is a chemical formula for an embodiment of a vinyl terminatedvinyl polysiloxane precursor material in accordance with the presentinventions.

FIG. 13 is a chemical formula for an embodiment of a hydride terminatedvinyl polysiloxane precursor material in accordance with the presentinventions.

FIG. 14 is a chemical formula for an embodiment of an allyl terminateddimethyl polysiloxane precursor material in accordance with the presentinventions.

FIG. 15 is a chemical formula for an embodiment of a vinyl terminateddimethyl polysiloxane precursor material in accordance with the presentinventions.

FIG. 16 is a chemical formula for an embodiment of a hydroxy terminateddimethyl polysiloxane precursor material in accordance with the presentinventions.

FIG. 17 is a chemical formula for an embodiment of a hydride terminateddimethyl polysiloxane precursor material in accordance with the presentinventions.

FIG. 18 is a chemical formula for an embodiment of a hydroxy terminatedvinyl polysiloxane precursor material in accordance with the presentinventions.

FIG. 19 is a chemical formula for an embodiment of a phenyl terminateddimethyl polysiloxane precursor material in accordance with the presentinventions.

FIG. 20 is a chemical formula for an embodiment of a phenyl and methylterminated dimethyl polysiloxane precursor material in accordance withthe present inventions.

FIG. 21 is a chemical formula for an embodiment of a methyl terminateddimethyl diphenyl polysiloxane precursor material in accordance with thepresent inventions.

FIG. 22 is a chemical formula for an embodiment of a vinyl terminateddimethyl diphenyl polysiloxane precursor material in accordance with thepresent inventions.

FIG. 23 is a chemical formula for an embodiment of a hydroxy terminateddimethyl diphenyl polysiloxane precursor material in accordance with thepresent inventions.

FIG. 24 is a chemical formula for an embodiment of a hydride terminateddimethyl diphenyl polysiloxane precursor material in accordance with thepresent inventions.

FIG. 25 is a chemical formula for an embodiment of a methyl terminatedphenylethyl polysiloxane precursor material in accordance with thepresent inventions.

FIG. 26 is a chemical formula for an embodiment of a tetravinylcyclosiloxane in accordance with the present inventions.

FIG. 27 is chemical formula for an embodiment of a trivinylcyclosiloxane in accordance with the present inventions.

FIG. 28 is a chemical formula for an embodiment of a divinylcyclosiloxane in accordance with the present inventions.

FIG. 29 is a chemical formula for an embodiment of a trivinyl hydridecyclosiloxane in accordance with the present inventions.

FIG. 30 is a chemical formula for an embodiment of a divinyl dihydridecyclosiloxane in accordance with the present inventions.

FIG. 31 is a chemical formula for an embodiment of a dihydridecyclosiloxane in accordance with the present inventions.

FIG. 32 is a chemical formula for an embodiment of a dihydridecyclosiloxane in accordance with the present inventions.

FIG. 33 is a chemical formula for an embodiment of a silane inaccordance with the present inventions.

FIG. 34 is a chemical formula for an embodiment of a silane inaccordance with the present inventions.

FIG. 35 is a chemical formula for an embodiment of a silane inaccordance with the present inventions.

FIG. 36 is a chemical formula for an embodiment of a silane inaccordance with the present inventions.

FIG. 37 is a chemical formula for an embodiment of a methyl terminateddimethyl ethyl methyl phenyl silyl silane polysiloxane precursormaterial in accordance with the present inventions.

FIG. 38 is chemical formulas for an embodiment of a polysiloxaneprecursor material in accordance with the present inventions.

FIG. 39 is chemical formulas for an embodiment of a polysiloxaneprecursor material in accordance with the present inventions.

FIG. 40 is chemical formulas for an embodiment of a polysiloxaneprecursor material in accordance with the present inventions.

FIG. 41 is a chemical formula for an embodiment of an ethyl methylphenyl silyl-cyclosiloxane in accordance with the present inventions.

FIG. 42 is a chemical formula for an embodiment of a cyclosiloxane inaccordance with the present inventions.

FIG. 43 is a chemical formula for an embodiment of a siloxane precursorin accordance with the present inventions.

FIGS. 43A to 43D are chemical formula for embodiments of the E₁ and E₂groups in the formula of FIG. 43.

FIG. 44 is a chemical formula for an embodiment of an orthosilicate inaccordance with the present inventions.

FIG. 45 is a chemical formula for an embodiment of a polysiloxane inaccordance with the present inventions.

FIG. 46 is a chemical formula for an embodiment of a triethoxy methylsilane in accordance with the present inventions.

FIG. 47 is a chemical formula for an embodiment of a diethoxy methylphenyl silane in accordance with the present inventions.

FIG. 48 is a chemical formula for an embodiment of a diethoxy methylhydride silane in accordance with the present inventions.

FIG. 49 is a chemical formula for an embodiment of a diethoxy methylvinyl silane in accordance with the present inventions.

FIG. 50 is a chemical formula for an embodiment of a dimethyl ethoxyvinyl silane in accordance with the present inventions.

FIG. 51 is a chemical formula for an embodiment of a diethoxy dimethylsilane in accordance with the present inventions.

FIG. 52 is a chemical formula for an embodiment of an ethoxy dimethylphenyl silane in accordance with the present inventions.

FIG. 53 is a chemical formula for an embodiment of a diethoxy dihydridesilane in accordance with the present inventions.

FIG. 54 is a chemical formula for an embodiment of a triethoxy phenylsilane in accordance with the present inventions.

FIG. 55 is a chemical formula for an embodiment of a diethoxy hydridetrimethyl siloxane in accordance with the present inventions.

FIG. 56 is a chemical formula for an embodiment of a diethoxy methyltrimethyl siloxane in accordance with the present inventions.

FIG. 57 is a chemical formula for an embodiment of a trimethyl ethoxysilane in accordance with the present inventions.

FIG. 58 is a chemical formula for an embodiment of a diphenyl diethoxysilane in accordance with the present inventions.

FIG. 59 is a chemical formula for an embodiment of a dimethyl ethoxyhydride siloxane in accordance with the present invention.

FIGS. 60A to 60F are chemical formulas for starting materials inaccordance with the present inventions.

FIG. 61 is an embodiment of a proppant preform forming and curing systemin accordance with the present invention.

FIG. 62 is a perspective view of a formation showing increased proppedarea and geometry for an embodiment of a PsDC in accordance with thepresent invention.

FIG. 63 is a chart showing the increase in natural gas production for anembodiment of a PsDC hydraulic fracture treatment in accordance with thepresent invention as compared to a conventional proppant.

FIG. 64 is a photograph of the fines created at 4 k API (ISO) crush testof an embodiment of proppants in accordance with the present invention.

FIG. 65 is a photograph of the fines created at 5 k API (ISO) crush testof an embodiment of proppants in accordance with the present invention.

FIG. 66 is a chart comparing the specific gravity and strength of anembodiment of a PsDC proppants in accordance with the present inventionwith conventional proppants (having specific gravities greater than2.5).

FIG. 67 is a chart comparing the settling rate of an embodiment of aPsDC proppants in accordance with the present invention withconventional proppants.

FIG. 68 is a chart comparing the particle size distribution for a batchof an embodiment of a PsDC proppant in accordance with the presentinvention with a batch of a conventional proppant.

FIG. 69 is a 400× magnification of an embodiment of a PsDC proppant inaccordance with the present inventions

FIG. 70 is a perspective view of an off shore well.

FIG. 71 is a cross sectional view of an off shore well.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

In general, the present inventions relate to synthetic proppants;methods for making these proppants; fracing fluids utilizing theproppants; and hydraulic fracturing methods.

In general, embodiments of the present inventions relate to polymericderived ceramic proppants; methods for making these proppants; fracingfluids utilizing these proppants; and hydraulic fracturing methods. Inparticular, the present inventions relate to proppants and hydraulicfracturing activities that utilize polymeric derived siloxane basedceramics, e.g., polysilocarb derived materials.

In general, embodiments of the present inventions further relate totreating wells, e.g., hydrocarbon producing wells, water wells andgeothermal wells, to increase and enhance the production from thesewells; and thus, for example, these embodiments relate to new hydraulicfracturing treatments and methods. Still more particularly, embodimentsof methods are provided for increasing the fluid conductivity between asubterranean formation containing a desired natural resource, e.g.,natural gas, crude oil, water, and geothermal heat source, and a well orborehole to transport the natural resource to the surface or a desiredlocation or collection point for that natural resource. For example,embodiments of the present inventions further relate to treating wells,e.g., hydrocarbon producing wells, water wells and geothermal wells, toincrease and enhance the production from these wells by syntheticproppant hydraulic fracturing treatments, including siloxane basedpolymeric derived ceramic proppant hydraulic fracturing, and includingpolysilocarb based polymer derived ceramic proppant hydraulicfracturing.

As used herein, unless specified otherwise, the terms “%”, “percent”,“weight %” and “mass %” and similar such terms are used interchangeablyand refer to the weight of a first component as a percentage of theweight of the total, e.g., batch, mixture or proppant. As used herein,unless specified otherwise “volume %” and “% volume” and similar suchterms refer to the volume of a first component as a percentage of thevolume of the total, e.g., batch, mixture or proppant. As used herein,unless specified otherwise, mesh size and mesh can be corresponded tothe relative diameters as set forth in Table 1. As used herein, unlessspecified otherwise: if particles are described as having a mesh size of“A” it means that the particles will pass through that mess, but will bestopped by a smaller mesh size; if particles are described as having amesh size of +(plus) mesh “A” it means that the particles will sit upon(e.g., be stopped by) the mesh “A” screen or sieve; and, if particlesare described as being − (minus) mesh “A” it means that the particleswill pass through (e.g., not be stopped by) the mesh “A” screen orsieve. When particle sizes, for a sample of proppants (a few 100proppants, to thousands of proppants, to millions of proppants, to tonsof proppants) are described as “A”/“B”, “A” denotes the largest size ofthe distribution of sizes, and “B” denotes the smallest size of thedistribution of sizes. Thus, a sample of proppants being characterizedas mesh 20/40 would have proppants that will pass through a 20 meshsieve, but will not pass through (i.e., are caught by, sit a top) a 40mesh sieve.

TABLE 1 U.S. Mesh Microns Millimeters (i.e., mesh) Inches (μm) (mm) 30.2650 6730 6.730 4 0.1870 4760 4.760 5 0.1570 4000 4.000 6 0.1320 33603.360 7 0.1110 2830 2.830 8 0.0937 2380 2.380 10 0.0787 2000 2.000 120.0661 1680 1.680 14 0.0555 1410 1.410 16 0.0469 1190 1.190 18 0.03941000 1.000 20 0.0331 841 0.841 25 0.0280 707 0.707 30 0.0232 595 0.59535 0.0197 500 0.500 40 0.0165 400 0.400 45 0.0138 354 0.354 50 0.0117297 0.297 60 0.0098 250 0.250 70 0.0083 210 0.210 80 0.0070 177 0.177100 0.0059 149 0.149 120 0.0049 125 0.125 140 0.0041 105 0.105 1700.0035 88 0.088 200 0.0029 74 0.074 230 0.0024 63 0.063 270 0.0021 530.053 325 0.0017 44 0.044 400 0.0015 37 0.037

Generally, the synthetic proppants and, any preforms, may be anypredetermined volumetric shape. The preform proppants may be the sameshape or a different shape from the final synthetic proppants. Thus, thepreforms, the proppants and both, may be shaped into balls, spheres,squares, prolate spheroids, ellipsoids, spheroids, eggs, cones, rods,boxes, multifaceted structures, and polyhedrons (e.g., dodecahedron,icosidodecahedron, rhombic triacontahedron, and prism), as well as,other structures or shapes. The synthetic proppants may be made into theshape of any proppant that has been used, has been suggested, is beingused, or may be developed in the future for use in hydraulic fracing, orin other similar types of operations. There shapes may also be random,such obtained from breaking up a block of material.

Spherical type structures are examples of a presently preferred shapefor proppants. Sphere and spherical shall mean, and include unlessexpressly stated otherwise, any structure that has at least about 90% ofits total volume within a “perfect sphere,” i.e., all points along thesurface of the structure have radii of equal distance. A spherical typestructure shall mean, and include all spheres, and any other structurehaving at least about 70% of its total volume within a perfect sphere.

Although this specification focuses on proppants, and in particularproppants for hydraulic fracturing, it is to be understood that thesmall volumetric shapes (preferably predetermined volumetric shapes) ofthe present materials, e.g., beads, etc., may have many other uses, inaddition to hydraulic fracturing, and that the scope of protection to beafford such materials is not limited to proppants, and hydraulicfracturing. These shapes can be many different sizes (for proppant, aswell as other uses), including any of the sizes on Table 1, and can belarger and smaller.

The batch formulations and processes of making synthetic proppantsprovides the ability to make proppants that are, among other shapes,spheres, perfect spheres, essentially perfect spheres (any otherstructure having at least about 98% of its total volume within a perfectsphere), and substantially perfect spheres (any other structure havingat least about 95% of its total volume within a perfect sphere).

Turning to FIG. 1 there is shown a scanning electron photo micrograph(SEPM) of an embodiment of a synthetic proppant of the presentinvention. The proppant is spherical, and has no porosity. The outersurface is smooth, uniform and solid. FIG. 2 shows a proppant of thesame type as FIG. 1 that has been subject to a load, of at least about12,000 psi or greater. The proppant has fractured and pieces of theproppant have fallen away, revealing the inner sections of the proppant,and showing that the proppant has no porosity, e.g., there are no voidsor pores (open or closed). The proppants of FIGS. 1 and 2 are polymerderived ceramic (PDC), and in particular, are polysilocarb derivedceramics (PsDC).

Embodiments of the synthetic proppant preferably have an apparentdensity that is close to, i.e., within 90% of the actual density of thematerial making up the proppant; more preferably the apparent density ofthe proppant is essentially the same as the actual density, i.e., within95% of the actual density, and still more preferably the apparentdensity of the proppant is the same as the actual density, i.e., within98% of the actual density. Thus, it is understood that apparent densitytakes into consideration (would include in the calculation) the voids ina structure if any; while actual density would not. For example, acommon sponge would have an apparent density that is significantly lowerthan its actual density. The absence of pores, or voids, from thestructure of the volumetric shapes is preferred, both absent from thesurface and from the interior.

The volumetric shapes of the synthetic proppants may also becharacterized by using a Krumbein and Sloss chart (FIG. 3) and analysis,which is a well known methodology by those of skill in the art, andwhich is also set forth in Section 7, “Proppant sphericity androundness” of ANSI/API Recommended Practice 19C, May 2008 (also ISO13503-2:2006). Under this characterization, the synthetic proppants mayhave average sphericity of at least about 0.5, at least about 0.7, atleast about 0.9, and greater. The synthetic proppants may have anaverage roundness of at least about 0.5, at least about 0.7, at leastabout 0.9 and greater. The siloxane derived ceramic proppants, e.g.,polysilocarb derived ceramic proppants, may have average sphericity ofat least about 0.5, at least about 0.7, at least about 0.9, and greater.The siloxane derived ceramic proppants, e.g., polysilocarb derivedceramic proppants, may have an average roundness of at least about 0.5,at least about 0.7, at least about 0.9 and greater. The polysiloxanederived ceramic proppants, e.g., polysilocarb derived ceramic proppants,may have average sphericity/roundness values of about ≧0.9/≧0.9,≧0.7/≧0.9, ≧0.9/≧0.7 and ≧0.7/≧0.7.

Synthetic proppants, e.g., polysilocarb derived ceramic proppants (“PsDCproppant”), may, for example, also have some, or all of, thecharacteristics set forth in Table 2, which characteristics are basedupon testing and methodologies that are well know in the art, and whichare also set forth in ANSI/API Recommended Practice 19C, May 2008 (alsoISO 13503-2:2006) as well as, API RP 56/58/60 (the entire disclosure ofeach of which is incorporated herein by reference). Generally, testingthat may be used in categorizing proppants can be found in, and is knownto those of skill in the art, in ANSI, API, and ISO, publications,reports, standards, etc., which collectively will be referred to hereinas “API (ISO).” Other additional testing and categorizations may beused, which generally known to those of skill in the art, or that areset forth in this specification. Embodiments of the present inventionscan exceed, out perform and both, one or more of the characteristics setforth in Table 2.

TABLE 2 More Characteristic/Physical Example PsDC PsDC PreferredPreferred Property 31 Example 1 Example 2 proppant proppant Range RangeTurbidity (NTU) 57 19 26 15 13 ≦250  ≦20   Krumbein Shape FactorsRoundness >0.9 >0.9 >0.9 0.7 0.7   ≧0.8  ≧0.95 Sphericity >0.9 >0.9 >0.9.07 0.8   ≧0.8  ≧0.95 Clusters (%) 0 0 0 1 0  ≦2 ≦1   Bulk Density(g/cc) 1.25 1.27 1.27 1.4 1.20 Bulk Density lbs/ft² 78.12 79.25 79.4487.40 74.91 Specific Gravity 2.1 2.09 2.12 1.90 1.70 2.1-1.0 1.8-1.3Particle size distribution Sieve  16 0.0 0.0 0.0 0.0 0.0  18 0.0 0.0 0.00.0 0.0  20 0.0 0.2 0.0 0.0 0.0  25 3.5 13.3 1.4 0.0 0.0  30 96.5 73.196.9 1 0.0  35 0.1 9.5 1.6 8 0.0  40 0.0 2.2 0.0 89 0.0  50 0.0 0.4 0.02 0.0  60 0.0 0.0 0.0 0.0 0.0  70 0.0 0.0 0.0 0.0 0.0  80 0.0 0.0 0.00.0 0.0  90 0.0 0.0 0.0 0.0 0.0 100 0.0 0.0 0.0 0.0 0.0 110 0.0 0.0 0.00.0 1 120 0.0 0.0 0.0 0.0 97 130 0.0 0.0 0.0 0.0 2 140 0.0 0.0 0.0 0.00.0 150 0.0 0.0 0.0 0.0 0.0 160 0.0 0.0 0.0 0.0 0.0 Pan 0.0 0.0 0.0 0.00.4   ≦1.0 ≦0.5 % in size 100 98.1 99.9 99 93  ≧95* ≧97**  Mean Particle0.659 0.653 0.655 0.400 0.149 1.680-0.053 0.841-0.074 Diameter mm MedianParticle 0.657 0.645 0.652 0.395 0.140 1.680-0.053 0.841-0.074 Diameter(MPD) mm Solubility in 12/3 3.5 3.1 2.4 3.5 3.8   ≦7.0 ≦4   HCL/HF for0.5 HR @ 150 F. (% weight loss) Solubility in 15% 0.2 1.8 0.3 0.4   ≦7.0≦4   HCL for 0.5 HR @ 150 F. (% weight loss) Settling Rate (ft/min)51.26 49.24 51.74 15.00 10.00 ≦30 ≦12   ISO crush Analysis 9.6 7.5 7.5≦10 ≦8.0 (% Fines) 4 lbs/ft² @ 4,000 psi ISO crush Analysis 13.2 9.7 9.16.7 ≦10 ≦8.0 (% Fines) 4 lbs/ft² @ 5,000 psi ISO crush Analysis 11.3 9.98.4 ≦10 ≦8.0 (% Fines) 4 lbs/ft² @ 6,000 psi ISO crush Analysis 8.6 108.9 ≦10 ≦8.0 (% Fines) 4 lbs/ft² @ 7,000 psi ISO crush Analysis 10.4 129.9 ≦10 ≦8.0 (% Fines) 4 lbs/ft² @ 8,000 psi Wettability (pH of FairFair Good Fair Wettable Fair or Water Extract) better pH of WaterExtract Initial pH 7.99 8.56 8.4 8.2 x x mL NaOH to pH 9 0.70 0.55 0.60.75 0.6 ± 0.2  0.6 ± 0.05 mL NaOH to pH 10 3.00 2.30 3.10 2.10 2.5 ±1.5 2.5 ± 0.5 mL NaOH to pH 11 6.20 6.10 6.25 6.0 6.0 ± 1   6.0 ± 0.5 ***for a particular targeted diameter sphere size within the targetedrange

The characteristics and physical properties identified in Table 2 arefurther explained as follows.

Turbidity—A measure to determine the levels of dust, silt, suspendedclay, or finely divided inorganic matter levels in fracturing proppants.High turbidity reflects improper proppant manufacturing and/or handlingpractices. The more often and more aggressively a proppant is handled,the higher the turbidity. Offloading pressures exceeding characteristicsor guidelines can have a detrimental effect on the proppant performance.Produced dust can consume oxidative breakers, alter fracturing fluid pH,and/or interfere with crosslinker mechanisms. As a result, higherchemical loadings may be required to control fracturing fluidrheological properties and performance. If fluid rheology is altered,then designed or modeled fracture geometry and conductivity will bealtered. A change in conductivity directly correlates to reservoir flowrate.

Krumbein Shape Factors—Determines proppant roundness and sphericity.Grain roundness is a measure of the relative sharpness of grain corners,or of grain curvature. Particle sphericity is a measure of how closely aproppant particle approaches the shape of a sphere. Charts developed byKrumbein and Sloss in 1963 are the most widely used method ofdetermining shape factors.

Clusters—Proppant grains should consist of single, well-roundedparticles. During the mining and manufacturing process of proppants,grains can attach to one another causing a cluster. It is recommended byISO 13503-2 that clusters be limited to less than 1% to be consideredsuitable for fracturing proppants.

Bulk Density—A dry test to gain an estimation of the weight of proppantthat will fill a unit volume, and includes both proppant and porosityvoid volume. This is used to determine the weight of a proppant neededto fill a fracture or a storage tank.

Specific Gravity—Also called Apparent Density, it includes internalporosity of a particle as part of its volume. It is measured with a lowviscosity fluid that wets the particle surface.

Sieve Analysis: Particle Size Distribution & Median ParticleDiameter—Also called a sieve analysis, this test determines the particlesize distribution of a proppant sample. Calibrated sieves are stackedaccording to ISO 13503-2 recommended practices and loaded with apre-measured amount of proppant. The stack is placed in a Ro-Tap sieveshaker for 10 minutes and then the amount on each sieve is measured anda percent by weight is calculated on each sieve. A minimum of 90% of thetested proppant sample should fall between the designated sieve sizes.Not over 0.1% of the total tested sample should be larger than the firstsieve size and not over 1.0% should fall on the pan. The in-sizepercent, mean particle diameter, and median particle diameter arecalculated, which relates directly to propped fracture flow capacity andreservoir productivity.

API/ISO Crush Test—The API test is useful for comparing proppant crushresistance and overall strength under varying stresses. A proppant isexposed to varying stress levels and the amount of fines is calculatedand compared to manufacturer specifications. A PT Crush Profile—can showgraphically how median particle diameter (MPD) can vary with changes inclosure stress. Unlike the ISO crush test, the PT Crush Profile uses theentire proppant sample for crushing at each stress, the sample is thensieved to determine particle distribution, and MPD is then calculated. Achange in MPD directly correlates to flow capacity and reservoirproductivity.

Acid Solubility—The solubility of a proppant in 12-3hydrochloric-hydrofluoric acid (HCl—HF) is an indication of the amountof undesirable contaminates. Exposing a proppant (specifically gravelpack/frac pack materials) may result in dissolution of part of theproppant, deterioration in propping capabilities, and a reduction infracture conductivity in the zone contacted by such acid. The loss offracture conductivity near the wellbore may cause a dramatic reductionin well productivity.

pH of Water Extract—This test reflects the potential chemical impact ofa proppant on fracturing fluid pH. Processing or manufacturing of priorart proppants can leave residues, or ‘free phenol’ in the case of resincoated proppants, which can interfere with polymer hydration rates,crosslinking mechanisms, etc. These effects if detected can usually beremedied by increasing buffering capacity, but if undetected can alterfracturing fluid rheology, change fracture geometry, and impact proppedfracture conductivity. A change in conductivity directly correlates toreservoir production rate.

Preferably the synthetic proppant has, minimal, little, to no affect onthe chemistry of the fracturing fluid, regardless of the differentadditives that can be in a fracturing fluid. In particular, it is highlypreferable that the synthetic proppant does not effect or change thechemistry of the fracturing fluid. The synthetic proppant many, inembodiments, provide enhancements or benefits, either chemical, physicalor both, to the fracturing fluid, e.g., reduced abrasion, increasedlubricity, buffering and specialty properties, e.g., by having aspecialty surface treatment, such as a biocide.

In general PsDC proppants essential have little to no affect on the pHof the fracturing fluid. Thus, they can be used with most, in not all,fracturing fluids and will not adversely affect or impact pH, buffering,or pH control, or intentional or planned pH variations, of the wellborefluids during the fracturing procedures. Further, the PsDC proppants maybe coated with, or otherwise contain pH control or solution bufferingmaterials, or sites, and in this manner help to control or maintain apredetermined pH for the fracturing fluids in the down hole environmentduring fracturing procedures or during production of hydrocarbons.

Regardless of the failure mechanism, fluid flow, or hydraulic mechanismstaking place, the synthetic proppants, e.g., PDC proppants, e.g., PsDCproppants exhibit surprising and exceptional performance features,including among other things improved strength to weight ratios, andimproved conductivities over prior art proppants.

For example, turning to FIG. 4, which is a chart comparing theshort-term conductivity data (line 450) for the proppant of Example 1with published long-term conductivity data for prior art proppants,Ottawa 451 (high grade sand), RCS 452 (resin coated sand), 453 LWCeramic (lightweight ceramic proppant), 454 ISP Ceramic (intermediatestrength proppant), and 455 HS Ceramic (high strength ceramic proppant).From the data present in FIG. 4 it can be seen that the proppant ofExample 1, 450, even though it had an API (ISO) crush test value of4,000 psi, exhibited superior conductivity to all prior art proppantsevaluated from closure of 5,000 psi to 15,000 psi.

Further, embodiments of synthetic proppants, e.g., PDC proppants, e.g.,PsDC proppants can exhibit conductivity data, at pressures about 5,000psi over its API (ISO) crush test rating: that are at least about 70% ofits conductivity data at its rated pressure; that are at least about 80%of its conductivity data at its rated pressure; that are at least about90% of its conductivity data at its rated pressure; and greater.Embodiments of PsDC proppants can exhibit conductivity data, atpressures about 10,000 psi over its API (ISO) crush test rating: thatare at least about 60% of its conductivity data at its rated pressure;that are at least about 70% of its conductivity data at its ratedpressure; that are at least about 80% of its conductivity data at itsrated pressure; and greater.

The enhanced conductivity data alone or in combination with otherenhanced features of embodiments of synthetic proppants, e.g., PDCproppants, e.g., PsDC proppants, such as sphericity, roundness, uniformsize distribution, and density provide for the potential for significantimprovements in both long-term and short-term in reservoir recovery,e.g., for enhanced initial production, short term and long termproduction of hydrocarbons from a well.

Thus, for example, performing a synthetic, e.g., PDC, e.g., PsDChydraulic fracture treatment, and thus having these proppants in thehydrocarbon reservoir, may for example provide benefits such asincreases in initial flow of the hydrocarbons, increases in the abilityto maintain those increased initial flows for extend or longer periodsof time over the life of the well, increase time when the well remainsproducing, increases in the ability to drain larger areas of a reservoirwith or from a single well, and combinations and variations of these andother benefits that may be realized through the use of syntheticproppants, e.g., PDC proppants, e.g., PsDC proppants in hydrocarbon,water and geothermal resources exploration and production.

Thus, for example, turning to FIG. 5 there is a table, and charted data500 showing the increase in propped area this is obtainable withembodiments of synthetic proppants, e.g., PDC proppants, e.g., PsDCproppants. The propped area can be increased by increasing the proppedfracture half-length (PFHL), shown by double-arrow 503, and byincreasing the propped height (PH), shown by double-arrow 502, andpreferably both. The increase in the propped area is shown by line 501.In the table and chart of FIG. 5, the expected performance of theproppant of Example 2 is compared against the performance of aconventional proppant. The proppant of Example 2 can have a 20% increasein PFHL and PH, which results in a 73% increase in total propped area.More preferably, the proppant of Example 2 can have a 50% increase inPFHL and PH, which results in a 237% increase in total propped area. Itis theorized that, among other reasons, because of the reduced density(both apparent and actual) of the synthetic proppants, e.g., PDCproppants, e.g., PsDC proppants, and their considerable increase instrength, for these reduced densities, the synthetic proppants arecapable of obtaining these significantly larger propped fracture areas,and thus significantly greater hydrocarbon production from a PsDChydraulically fractured well than can be obtained from prior proppantsand fracturing treatments.

Turning to FIG. 6, the increase in both PFHL, as well as PH that can beachieved from using the PsDC proppant of Example 2 is illustrated. Awell 601 in a formation 600 has a lateral section 605. The lateralsection 605 has three zones that are perforated and subjected to a PsDChydraulic fracturing treatment. The propped area for the PsDC hydraulicfracturing treatments, 602 a, 603 a, 604 a, is substantially larger thanthe maximum propped area, 602 b, 603 b, 604 b that could be obtainedwith conventional proppants.

Thus, the PsDC hydraulic fracturing treatments provide the ability toincrease the Initial Product (IP) from the well (e.g., the amount ofproduction that the well produces during an initial time periodtypically, about 90 days, about 180 days, and generally less than 1year), to increase the Decline Curve Reduction (DCR) for the well (e.g.,generally over time the amount of production from a well declines overtime, slowing this decline in production is viewed as an increase in theDCR), and both. Turning to FIG. 7 there is shown a chart 700 showing theeffect on total production that can be obtained from PsDC hydraulicfracturing treatments. In FIG. 7 there is shown a chart 700 showingpotential increases in DCR 701 and IP & DCR 702, and the effect theseincreases have on total production from the well over a 10 year period.Thus, embodiments of the PsDC hydraulic fracturing treatments have theability to increase the 10 year production of a well by at least about20%, at least about 30% at least about 60%, at least about 100% andmore.

In general, unless specifically stated otherwise, the percentageincreases, improved performance, and other comparisons that are made inthis specification to current and prior art proppants, fracturingtechnologies, and treatments, are based upon modeling, predictions, dataand calculations known to those of skill in the art for providing theproduction and performance features for a well that is treated with suchcurrent or prior art technologies.

The processes and the formulations used to make the synthetic proppants,e.g., PDC proppants, e.g., PsDC proppants, provide the ability to makeproppants having a very narrow particle size distribution. Thus,embodiments of these processes produce proppants that are within atleast 90% of the targeted size, at least 95% of the targeted size, andat least 99% of the targeted size. For example, the process can producespherical proppant, spherical type proppants, essentially perfectspherical proppant, and substantially perfect spherical proppant, eachof which can have at least about 90% of their size within a 10 meshrange, at least about 95% of their size within a 10 mesh range, at leastabout 98% of their size within a 10 mesh range, and at least about 99%of their size within a 10 mesh range. Further, and for example, theprocess can produce spherical proppant, spherical type proppants,essentially perfect spherical proppant, and substantially perfectspherical proppant, each of which can have at least about 90% of theirsize within a 5 mesh range, at least about 95% of their size within a 5mesh range, at least about 98% of their size within a 5 mesh range, andat least about 99% of their size within a 5 mesh range. Preferably,these levels of uniformity in the production of the synthetic proppants,e.g., PDC proppants, e.g., PsDC proppants, is obtained without the needfor filtering, sorting or screening the cured proppants, and without theneed for filtering, sorting or screening the pyrolized proppants. Inaddition to having the ability to tightly control size distribution,embodiments of the present processes and formulations provide theability to make a large number of highly uniform predetermined shapes,e.g., at least about 90%, at least about 95% and at least about 99% ofthe proppants have a predetermined sphericity and/or roundness. Forexample, at least about 98% of the proppants made from a batch can beessentially spherical.

In FIG. 8 there is shown a perspective view of a synthetic, e.g., PDC,e.g., PsDC hydraulic fracturing site 800. Thus, positioned near the wellhead 814 there are, pumping trucks 806, proppant, e.g., PsDc proppant,storage containers 810, 811, a proppant feeder assembly 809, a mixingtruck 808, and fracturing fluid holding units 812. It is understood thatFIG. 8 is an illustration and simplification of a fracturing site. Suchsites may have more, different, and other pieces of equipment such aspumps, holding tanks, mixers, and chemical holding units, mixing andaddition equipment, lines, valves and transferring equipment, as well ascontrol and monitoring equipment.

A high-pressure line 805 that transfers high pressure fracturing fluidfrom the pump trucks 806 into the well. The wellhead 804 may also havefurther well control devices associated with it, such as a BOP.Fracturing fluid from holding units 812 is transferred through lines 813to mixing truck 808, where proppant from storage containers 810, 811 isfeed, (metered in a controlled fashion) by assembly 809 and mixed withthe fracturing fluid. The fracturing fluid and proppant mixture is thentransferred to the pump trucks 806, by line 803, where the pump trucks806 pump the fracturing fluid into the well by way of high pressure line805.

In embodiments, the PsDCs are mixed with fracing fluids for down holehydraulic fracturing operations to, for example, recover hydrocarbons,such as crude oil and natural gas. Typically, between about 0.1 andabout 12 lbs/gal, between about 3 and about 10 lbs/gal, between about0.1 and about 1 lbs/gal, between about 1.1 and about 2 lbs/gal, betweenabout 2.1 and about 4 lbs/gal, and between about 3.1 and about 8 lbs/galof PsDC are mixed into fracing fluid, greater and lesser amounts thanabout 12 lbs/gal and about 1 lbs/gal are also contemplated. Typically,at least about 10,000 gals, at least about 100,000 gals, at least about1,000,000 gals and more of fracing fluid are used in a fracingoperation. Thus, in general hundreds of thousands, if not millions ofpounds of proppant, e.g., PsDC proppant, could be used in a singlehydraulic fracturing operation.

The highly uniform nature of embodiments of the present proppantsprovides for many new and previously unavailable advantageous ways tometer and add in a controlled manner, the proppant to fracturing fluid,for a fracturing treatment. The proppant can be added using volumetricmeasurements, or metering systems, instead of weight based meteringsystem of the prior art. Volumetric systems using embodiments of thepresent proppants provides the same or greater level of control because,among other things, the proppants of the present invention are highlyuniform and thus volume of these proppants equates linearly, and withhigh predictability, to the weight of the proppants. This ability tometer, in a controlled manner, by volume, the proppants of the presentinventions provides the ability to add these proppants in a controlledmanner to the well head, to the high pressure line, and generally, afterthe high pressure, high volume pumps. Such addition will greatly reducethe wear on the pumps and increase their lives.

Because such large volumes of proppants are used in these operations,and because of the importance in understanding and knowing thecharacteristics of the proppant, both on a micro level (e.g., a singlespherical type structure) and on the macro level (e.g., how the proppantpack behaves in the down hole environment) sampling methods have beendeveloped and are well know in the art to obtain representative samplesfor testing and characterization of a larger volume of proppant, e.g., alot, a load, a rail car, etc. These sampling methods are set forth inAPI RP 56, ISO 13503-2:2006, and in ANSI/API Recommended Practice 19C,First Edition, May 2008. Unless expressly stated otherwise, or contraryto the context, as used herein, when PsDC characteristics, properties,or both are used they will refer to a representative sample of theproppant.

Generally, in the manufacture of PsDCs a polysilocarb batch is formedinto a preform proppant. Depending upon the viscosity and othercharacteristics of the polysilocarb batch, and the intended shape of theproppant, the preform may be made by techniques such as extruding,molding, drawing, spinning, dripping, spraying, vibrating, polymeremulsion (emulsion polymerization, including micro-emulsionpolymerization, capable of making a substantial range of sizes, e.g.,from about 10 mesh to about 400 mesh, from about 20 mesh to about 200mesh, from about 500 microns and less, from about 50 microns and less,from about 10 microns and less) and other techniques known to the artsto create small structures of a predetermined shape, and preferably inlarge volumes, preferably that are highly uniform and more preferablyboth. Further it is understood, that although it is presently preferredthat the preform and the proppant be their approximate size and shapeupon cure, or prior to pyrolysis, the polysilocarb batch can be curedinto a puck like structure, e.g., roughly the size and shape of a hockeypuck, a brick like structure or other larger volumetric shape. Thislarger shape can be cured, hard cured, and pyrolized, and broken downinto smaller sizes (preferably after pyrolysis). This process of laterbreaking down, typically, although not necessarily, results in aproppant that is not of uniform or consistent shape, size and both.

The curing process may take place upon initial forming, if the preformis unrestrained, to make certain that the predetermined shape is locked,e.g., fixed or set, so that later handing of the preform will not changethe shape. The curing process may be continuous, e.g., initial cure tohard cure occurs in one time period and process, or may take place inseveral stages, e.g., an initial cure for a set time period andtemperature, a cure of a set time period and temperature, and a hardcure for a set time period and temperature. These cure stages may takeplace back-to-back with no intervening time periods or they may bestaggered in time, with intervening time periods where the preform ismaintained at ambient temperature, or where the preform is subjected tosome other process. For example, an initial cure may be performed, acure may then be performed, in which case the preform has the appearanceof having a hard skin with gelatinous center, at which point the preformcould be subjected to a shaping operation to get it into is final form,at which point the hard cure would be performed.

In general, and for example, for the purposes of making beads, or ballshaped proppants one or more of the process parameters and equipment setforth in table 3 can be used.

TABLE 3 Nozzle Thermal Heat Exchanger Curing Process Production ofproppant Temperature range 0 to Temperature beads thru the use ofinternal 1600 C. multi zone/range range 0 to 1600 and external orifices,controlled C. multi atomization mechanically, zone/range con- pressure,and gas to produce trolled (manually tight mesh distribution orautomated - (within 1 to 5 mesh sizes of local or remote) target size)beads ranging from 2000 micron to 75 micron. Produced thru the use of aAir, Steam, Electrical, Phased curing temperature compensated Gas, WasteHeat, or process in part or (liquid, air, gas, radiant, or Solar sourceof heat whole mechanical) controllable one or more active orifices orfilament, (vibration, heat, pressure, pulsation, 20 Hz to 20,000 Hzfrequency) Orifices or filament Material of Air or inert gas material;made from metal, Construction—metallic, controlled composite, plastic,precious composite, fire brick, or atmosphere metal, jewel, or ceramic,ceramic Gravity or pressure Radiant, convection, Air, Steam, compensatedorifices direct heat, Electrical, Gas, or filament Waste Heat, or Solarsource of heat Continuous operation and Vertical to horizontal Heattransferring flow; or batch process orientations media of air, inertgas, radiant, con- vection, con- densing, vapor, or direct heatViscosity range 1 to 1000 Up to and including Multi Chambered Adiabaticenabled or portioned Static and dynamic particle 1′ to 500′ StructureContinuous and processing Height batch Multi Chambered or Static andportioned dynamic particle processing Heat transferring media of air,inert gas, radiant, convective, condensing, vapor or direct heat Staticand dynamic particle processing

Turning to FIG. 9 there is provided a schematic flow diagram of anembodiment of a proppant preform forming and curing system 900. Thesystem 900 has a precursor batch preparation system 901, which is usedto blend, mix, catalyze, or other preparation steps that may beperformed to prepare the precursor batch for forming and curing. Thesepreparation steps and systems are taught and disclosed in U.S. patentapplication Ser. No. 14/268,150, the entire disclosure of which isincorporated herein by reference. A transfer line 902 transfers theprecursor batch to a formation device 903, which forms the precursorbatch into a shape of the proppant. The shaped precursor is then curedin curing device 904 to a preform, or preform proppant. (It should benoted that preparation steps may occur along the transfer line 902, andat the formation device 903.) The cured preformed proppants are thentransferred by transfer device 905 (which may not be present, could be acontinuous system such as a conveyor system, or air pressure transfersystem, a batch system, including hand pushed bins) to the pyrolysisdevice 906. In the pyrolysis device 906 the preform proppants arepyrolized to from a ceramic, e.g. the PsDC proppants. The pyrolysis maybe continuous, semi-continuous, or batch. It may take place in an inertatmosphere, an inert reduced pressure atmosphere, a vacuum, air, aflowing inert atmosphere, a flowing reduced pressure atmosphere, andcombinations and variations of these. Post cure processing station 910 aand post pyrolysis processing station 910 b my be used to perform stepssuch as sorting, filtering, sieving, inspecting, washing, drying,treating, coating, and combinations of these and other post processingsteps. Transfer device 907 transfers the finished proppants to a storageand delivery station 908, where the finished proppant can be transferredinto shipping devices 909, e.g. a truck, container, barge or rail car.

In general, preferred embodiments of the synthetic proppants of thepresent inventions are made from unique and novel silicon (Si) basedmaterials that are easy to manufacture, handle and have surprising andunexpected properties and applications. These silicon based materials goagainst the general trends of the art of silicon chemistry and uses.Generally, the art of silicon chemistry, and in particular organosiliconchemistry, has moved toward greater and greater complexity in thefunctional groups that are appended to, and a part of, a silicon basedpolymeric backbone. Similarly, in general, the processes that areutilized to make these polymers have moved toward greater and greatercomplexity. Embodiments of the present new material systems for use asproppants move away from this trend, by preferably functionalizing asilicon based polymeric backbone with simpler structures, such asphenyl, phenylethyl and smaller groups, and do so with processes thatare simplified, e.g., solvent free, reduced solvent, lower cost startingmaterials, fewer steps, and reduction of reaction intermediates.

Further, and generally, the art views silicones as tacky, soft or liquidmaterials that are used with, on, or in conjunction with, othermaterials to enhance or provide a performance feature to those othermaterials. Silicon based materials generally are not viewed as standalone products, primary products, or structural elements. The preferredsilicon based materials for use as proppants, however, move away fromthis trend and understanding in the art. These silicon based materialsprovide materials that are exceptionally strong, and can function asstand alone products and composites, among other things.

Generally, preferred embodiments of the synthetic proppants of thepresent inventions are directed to polymer derived ceramics (PDC), andmore preferably toward “polysilocarb” materials, e.g., materialcontaining silicon (Si), oxygen (O) and carbon (C), and materials thathave been pyrolized from such materials. Polysilocarb materials may alsocontain other elements. Polysilocarb materials are made from one or morepolysilocarb precursor formulation or precursor formulation. Thepolysilocarb precursor formulation contains one or more functionalizedsilicon polymers, or monomers, as well as, potentially otheringredients, such as for example, inhibitors, catalysts, pore formers,fillers, reinforcers, fibers, particles, colorants, pigments, dies,polymer derived ceramics (“PDC”), ceramics, metals, metal complexes, andcombinations and variations of these and other materials and additives.

The precursor batch may also contain non-silicon based cross linkingagents, that are intended to, provide, the capability to cross-linkduring curing. For example, cross linking agents that can be usedinclude DCPD—dicylcopentadiene, 1,4 butadiene, divnylbenzene, Isoprene,norbornadiene, propadiene, 4-vinylcyclohexene, 2-3 heptadiene 1, 3butadiene and cyclooctadiene. Generally, any hydrocarbon that containstwo (or more) unsaturated, C═C bonds that can react with a Si—H, Si—OH,or other Si bond in a precursor, can be used as a cross linking agent.Some organic materials containing oxygen, nitrogen, and sulphur may alsofunction as cross linking moieties.

The polysilocarb precursor formulation is then cured to form a solid orsemi-sold material, e.g., a plastic. The polysilocarb precursorformulation may be processed through an initial cure, to provide apartially cured material, which may also be referred to, for example, asa preform, green material, or green cure (not implying anything aboutthe material's color). The green material may then be further cured.Thus, one or more curing steps may be used. The material may be “endcured,” i.e., being cured to that point at which the material has thenecessary physical strength and other properties for its intendedpurpose. The amount of curing may be to a final cure (or “hard cure”),i.e., that point at which all, or essentially all, of the chemicalreaction has stopped (as measured, for example, by the absence ofreactive groups in the material, or the leveling off of the decrease inreactive groups over time). Thus, the material may be cured to varyingdegrees, depending upon its intended use and purpose. For example, insome situations the end cure and the hard cure may be the same.

The curing may be done at standard ambient temperature and pressure(“SATP”, 1 atmosphere, 25° C.), at temperatures above or below thattemperature, at pressures above or below that pressure, and over varyingtime periods (both continuous and cycled, e.g., heating followed bycooling and reheating), from less than a minute, to minutes, to hours,to days (or potentially longer), and in air, in liquid, or in apreselected atmosphere, e.g., Argon (Ar) or nitrogen (N₂).

The polysilocarb precursor formulations can be made into non-reinforced,non-filled, composite, reinforced, and filled structures, intermediatesand end products, and combinations and variations of these and othertypes of materials. Further, these structures, intermediates and endproducts can be cured (e.g., green cured, end cured, or hard cured),uncured, pyrolized to a ceramic, and combinations and variations ofthese (e.g., a cured material may be filled with pyrolized beads derivedfrom the same polysilocarb as the cured material).

The precursor formulations may be used to form “neat” materials, (by“neat” material it is meant that all, and essentially all of thestructure is made from the precursor material or unfilled formulation;and thus, there are no fillers or reinforcements). They may be used toform composite materials, e.g., reinforced products. They may be used toform non-reinforced materials, which are materials that are made ofprimarily, essentially, and preferably only from the precursormaterials.

In making the polysilocarb precursor formulation into a volumetric shapeor structure, the polysilocarb formulation can be, for example, sprayed,spray dried, emulsified, polymer emulsification, polymermicro-emulsification, thermally sprayed, molded, flowed, formed,extruded, spun, dropped, injected or otherwise manipulated intoessentially any volumetric shape, including the shapes for the proppant,and combinations and variations of these. These volumetric shapes wouldinclude, for example, spheres, pellets, rings, lenses, disks, panels,cones, frustoconical shapes, squares, rectangles, trusses, angles,channels, hollow sealed chambers, hollow spheres, blocks, sheets,coatings, films, skins, particulates, beams, rods, angles, columns,fibers, staple fibers, tubes, cups, pipes, and combinations and variousof these and other more complex shapes, both engineering andarchitectural. Additionally, they may be shaped into preforms, orpreliminary shapes that correspond to, or with, a final product, such asfor example use in or with, a break pad, a clutch plate, a break shoe, amotor, high temperature parts of a motor, a diesel motor, rocketcomponents, turbine components, air plane components, space vehiclecomponents, building materials, shipping container components, and otherstructures or components.

The polysilocarb precursor formulations may be used with reinforcingmaterials to form a composite material. Thus, for example, theformulation may be flowed into, impregnated into, absorbed by orotherwise combined with a reinforcing material, such as carbon fibers,glass fiber, woven fabric, non-woven fabric, copped fibers, fibers,rope, braided structures, ceramic powders, glass powders, carbonpowders, graphite powders, ceramic fibers, metal powders, carbidepellets or components, staple fibers, tow, nanostructures of the above,PDCs, any other material that meets the temperature requirements of theprocess and end product, and combinations and variations of these. Thus,for example, the reinforcing materials may be any of the hightemperature resistant reinforcing materials currently used, or capableof being used with, existing plastics and ceramic composite materials.Additionally, because the polysilocarb precursor formulation may beformulated for a lower temperature cure (e.g., SATP) or a curetemperature of for example about 100° F. to about 400° F., thereinforcing material may be polymers, organic polymers, such as nylons,polypropylene, and polyethylene, as well as aramid fibers, such as NOMEXor KEVLAR.

The reinforcing material may also be made from, or derived from the samematerial as the formulation that has been formed into a fiber andpyrolized into a ceramic, or it may be made from a different precursorformulation material, which has been formed into a fiber and pyrolizedinto a ceramic. In addition to ceramic fibers derived from the precursorformulation materials that may be used as reinforcing material, otherporous, substantially porous, and non-porous ceramic structures derivedfrom a precursor formulation material may be used.

The polysilocarb precursor formulation may be used to form a filledmaterial. A filled material would be any material having other solid, orsemi-solid, materials added to the polysilocarb precursor formulation.The filler material may be selected to provide certain features to thecured product, the ceramic product or both. These features may relate toor be aesthetic, tactile, thermal, density, radiation, chemical,magnetic, electric, and combinations and variations of these and otherfeatures. These features may be in addition to strength. Thus, thefiller material may not affect the strength of the cured or ceramicmaterial, it may add strength, or could even reduce strength in somesituations. The filler material could impart color, magneticcapabilities, fire resistances, flame retardance, heat resistance,electrical conductivity, anti-static, optical properties (e.g.,reflectivity, refractivity and iridescence), aesthetic properties (suchas stone like appearance in building products), chemical resistivity,corrosion resistance, wear resistance, abrasions resistance, thermalinsulation, UV stability, UV protective, and other features that may bedesirable, necessary, and both, in the end product or material. Thus,filler materials could include copper lead wires, thermal conductivefillers, electrically conductive fillers, lead, optical fibers, ceramiccolorants, pigments, oxides, dyes, powders, ceramic fines, PDCparticles, pore-formers, carbosilanes, silanes, silazanes, siliconcarbide, carbosilazanes, siloxane, powders, ceramic powders, metals,metal complexes, carbon, tow, fibers, staple fibers, boron containingmaterials, milled fibers, glass, glass fiber, fiber glass, andnanostructures (including nanostructures of the forgoing) to name a few.

The fill material may also be made from, or derived from the samematerial as the formulation that has been formed into a cured orpyrolized solid, or it may be made from a different precursorformulation material, which has been formed into a cured solid orsemi-solid, or pyrolized solid.

The polysilocarb formulation and products derived or made from thatformulation may have metals and metal complexes. Thus, metals as oxides,carbides or silicides can be introduced into precursor formulations, andthus into a silica matrix in a controlled fashion. Thus, usingorganometallic, metal halide (chloride, bromide, iodide), metal alkoxideand metal amide compounds of transition metals and then copolymerizingin the silica matrix, through incorporation into a precursor formulationis contemplated.

For example, Cyclopentadienyl compounds of the transition metals can beutilized. Cyclopentadienyl compounds of the transition metals can beorganized into two classes: Bis-cyclopentadienyl complexes; andMono-cyclopentadienyl complexes. Cyclopentadienyl complexes can includeC₅H₅, C₅Me₅, C₅H₄Me, CH₅R₅ (where R=Me, Et, Propyl, i-Propyl, butyl,Isobutyl, Sec-butyl). In either of these cases Si can be directly bondedto the Cyclopentadienyl ligand or the Si center can be attached to analkyl chain, which in turn is attached to the Cyclopentadienyl ligand.

Cyclopentadienyl complexes, that can be utilized with precursorformulations and in products, can include: bis-cyclopentadienyl metalcomplexes of first row transition metals (Titanium, Vanadium, Chromium,Iron, Cobalt, Nickel); second row transition metals (Zirconium,Molybdenum, Ruthenium, Rhodium, Palladium); third row transition metals(Hafnium, Tantalum, Tungsten, Iridium, Osmium, Platinum); Lanthanideseries (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho); Actinide series(Ac, Th, Pa, U, Np).

Monocyclopentadienyl complexes may also be utilized to provide metalfunctionality to precursor formulations and would includemonocyclopentadienyl complexes of: first row transition metals(Titanium, Vanadium, Chromium, Iron, Cobalt, Nickel); second rowtransition metals (Zirconium, Molybdenum, Ruthenium, Rhodium,Palladium); third row transition metals (Hafnium, Tantalum, Tungsten,Iridium, Osmium, Platinum) when preferably stabilized with properligands, (for instance Chloride or Carbonyl).

Alky complexes of metals may also be used to provide metal functionalityto precursor formulations and products. In these alkyl complexes the Sicenter has an alkyl group (ethyl, propyl, butyl, vinyl, propenyl,butenyl) which can bond to transition metal direct through a sigma bond.Further, this would be more common with later transition metals such asPd, Rh, Pt, Ir.

Coordination complexes of metals may also be used to provide metalfunctionality to precursor formulations and products. In thesecoordination complexes the Si center has an unsaturated alkyl group(vinyl, propenyl, butenyl, acetylene, butadienyl) which can bond tocarbonyl complexes or ene complexes of Cr, Mo, W, Mn, Re, Fe, Ru, Os,Co, Rh, Ir, Ni. The Si center may also be attached to a phenyl,substituted phenyl or other aryl compound (pyridine, pyrimidine) and thephenyl or aryl group can displace carbonyls on the metal centers.

Metal alkoxides may also be used to provide metal functionality toprecursor formulations and products. Metal alkoxide compounds can bemixed with the Silicon precursor compounds and then treated with waterto form the oxides at the same time as the polymer, copolymerize. Thiscan also be done with metal halides and metal amides. Preferably, thismay be done using early transition metals along with Aluminum, Galliumand Indium, later transition metals: Fe, Mn, Cu, and alkaline earthmetals: Ca, Sr, Ba, Mg.

Compounds where Si is directly bonded to a metal center which isstabilized by halide or organic groups may also be utilized to providemetal functionality to precursor formulations and products.

Additionally, it should be understood that the metal and metal complexesmay be the continuous phase after pyrolysis, or subsequent heattreatment. Formulations can be specifically designed to react withselected metals to in situ form metal carbides, oxides and other metalcompounds, generally known as cermets (e.g., ceramic metalliccompounds). The formulations can be reacted with selected metals to formin situ compounds such as mullite, alumino silicate, and others. Theamount of metal relative to the amount of silica in the formulation orend product can be from about 0.1 mole % to 99.9 mole %, about 1 mole %or greater, about 10 mole % or greater, about 20 mole percent or greater% and greater. The forgoing use of metals with the present precursorformulas can be used to control and provide predeterminedstoichiometries.

Filled materials would include reinforced materials. In many cases,cured, as well as pyrolized polysilocarb filled materials can be viewedas composite materials. Generally, under this view, the polysilocarbwould constitute the bulk or matrix phase, (e.g., a continuous, orsubstantially continuous phase), and the filler would constitute thedispersed (e.g., non-continuous), phase.

It should be noted, however, that by referring to a material as “filled”or “reinforced” it does not imply that the majority (either by weight,volume, or both) of that material is the polysilcocarb. Thus, generally,the ratio (either weight or volume) of polysilocarb to filler materialcould be from about 0.1:99.9 to 99.9:0.1. Smaller amounts of fillermaterial or polysilocarb could also be present or utilized, but wouldmore typically be viewed as an additive or referred to in other manners.Thus, the terms composite, filled material, polysilocarb filledmaterials, reinforced materials, polysilocarb reinforced materials,polysilocarb filled materials, polysilocarb reinforced materials andsimilar such terms should be viewed as non-limiting as to amounts andratios of the material's constitutes, and thus in this context, be giventheir broadest possible meaning.

The polysilocarb precursor formulation may be specifically formulated tocure under conditions (e.g., temperature, and perhaps time) that match,e.g., are predetermined to match, the properties of the reinforcingmaterial, filler material or substrate. These materials may also be madefrom, or derived from, the same material as the polysilocarb precursorformulation that is used as the matrix, or it may be made from adifferent polysilocarb precursor formulation. In addition to ceramicfibers derived from the polysilocarb precursor formulation materials,porous, substantially porous, and non-porous ceramic structures derivedfrom a polysilocarb precursor formulation material may be used as filleror reinforcing material.

The polysilocarb precursor formulations may be used to coat orimpregnate a woven or non-woven fabric, made from for example carbonfiber, glass fibers or fibers made from a polysilocarb precursorformulation (the same or different formulation), to from a prepregmaterial. Further, a polysilocarb precursor formulation may be used asan interface coating on the reinforcing material, for use either with apolysilocarb precursor formulation as the matrix material. Further,carbon fiber may be heat treated to about 1,400° to about 1,800° orhigher, which creates a surface feature that eliminates the need for aseparate interface coating, for use with polysilocarb precursorformulations.

Fillers can reduce the amount of shrinkage that occurs during theprocessing of the formulation into a ceramic, they can be used toprovide a predetermined density of the product, either reducing orincreasing density, and can be used to provide other customized andpredetermined product and processing features. Fillers, at largeramounts, e.g., greater than 10%, can have the effect of reducingshrinkage during cure.

Depending upon the particular application, product or end use, thefiller can be evenly distributed in the precursor formulation, unevenlydistributed, a predetermined rate of settling, and can have differentamounts in different formulations, which can then be formed into aproduct having a predetermined amounts of filler in predetermined areas,e.g., striated layers having different filler concentration.

Preferably, for a typical filled product, the filler is substantiallyevenly distributed and more preferably evenly distributed within the endproduct. In this manner localize stresses or weak points can be avoided.Generally, for a non-reinforced material each filler particle may have avolume that is less than about 0.3%, less than about 0.2%, less thanabout 0.1%, and less than about 0.05% of the volume of a product,intermediate or proppant. For example, if the product is spherical inshape and the filler is spherical in shape the diameter of the fillershould preferable be about 1/10 to about 1/20 of the diameter of theproppant particle, and more preferably the filler diameter should beless than about 1/20 of the diameter of the proppant particle.Generally, the relative amount of filler used in a material shouldpreferable be about 30% to about 65% of the volume of the sphere, e.g.,volume %.

Generally, when a small particulate filler, e.g., fines, beads, pellets,is used for the purposes of increasing strength, without the presence offibers, fabric, etc., generally at least about 2% to at least about 5volume %, can show an increase in the strength, although this may begreater or smaller depending upon other factors, such as the shape andvolume of the product, later processing conditions, e.g., cure time,temperature, number of pyrolysis reinfiltrations. Generally, as thefiller level increases from about above 5 volume % no further strengthbenefits may be realized. Such small particulate filled products, inwhich appreciable strength benefits are obtained from the filler, and inparticular an increase in strength of at least about 5%, at last about10% and preferably at least about 20% would be considered to bereinforced products and materials.

At various points during the manufacturing process, the polysilocarbstructures, intermediates and end products, and combinations andvariations of these, may be machined, milled, molded, shaped, broken,drilled or otherwise mechanically processed and shaped.

The precursor formulations are preferably clear or are essentiallycolorless and generally transmissive to light in the visiblewavelengths. They may, depending upon the formulation have a turbid,milky or clouding appearance. They may also have color bodies, pigmentsor colorants, as well as color filler (which can survive pyrolysis, forceramic end products, such as those used in ceramic pottery glazes). Theprecursor may also have a yellow or amber color or tint, without theneed of the addition of a colorant.

The precursor formulations may be packaged, shipped and stored for lateruse in forming products, e.g., proppants, or they may be used directlyin these processes, e.g., continuous process to make a proppant. Thus, aprecursor formulation may be stored in 55 gallon drums, tank trucks,rail tack cars, onsite storage tanks having the capable of holdinghundreds of gals, and shipping totes holding 1,000 liters, by way ofexample. Additionally, in manufacturing process the formulations may bemade and used in a continuous, and semi-continuous processes.

The present inventions, among other things, provide substantialflexibility in designing processes, systems, ceramics, having processingproperties and end product performance features to meet predeterminedand specific performance criteria. Thus, for example the viscosity ofthe precursor formulation may be predetermined by the formulation tomatch a particular morphology of the reinforcing material, the curetemperature of the precursor formulation may be predetermined by theformulation to enable a prepreg to have an extended shelf life. Theviscosity of the of the precursor formulation may be established so thatthe precursor readily flows into the processing head, e.g., a sonicnozzle. The formulation of the precursor formulation may also, forexample, be such that the strength of a cured preform is sufficient toallow rough or initial processing of the preform, prior to pyrolysis,e.g., breaking up of a puck to provide small, e.g., about 10 mmdiameters to about 10 micron diameters, and potentially smaller to themicron and submicron diameter size.

Custom and predetermined control of when chemical reactions occur in thevarious stages of the process from raw material to final end product canprovide for reduced costs, increased process control, increasedreliability, increased efficiency, enhanced product features, andcombinations and variation of these and other benefits. The sequencingof when chemical reactions take place can be based primarily upon theprocessing or making of precursors, and the processing or making ofprecursor formulations; and may also be based upon cure and pyrolysisconditions. Further, the custom and predetermined selection of thesesteps, formulations and conditions, can provide enhanced product andprocessing features through chemical reactions, molecular arrangementsand rearrangements, and microstructure arrangements and rearrangements,that preferably have been predetermined and controlled.

It should be understood that the use of headings in this specificationis for the purpose of clarity, and are not limiting in any way. Thus,the processes and disclosures described under a heading should be readin context with the entirely of this specification, including thevarious examples. The use of headings in this specification should notlimit the scope of protection afford the present inventions.

Generally, the process form making the present polysilocarb materialsinvolves one or more steps. The starting materials are obtained, made orderived. Precursors are obtained or can be made from starting materials.The precursors are combined to form a precursor formulation. Theprecursor formulation is then shaped, dropped, extruded, sprayed,formed, molded, etc. into a desired form, which form is then cured,which among other things transforms the precursor formulation into aplastic like material. This cured plastic like material can then bepyrolyzed into a ceramic. It being understood, that these steps may notall be used, that some of these steps may be repeated, once, twice orseveral times, and that combinations and variations of these generalsteps may be utilized to obtain a desired product or result.

Processes for Obtaining a Polysilocarb Precursor Formulation

Polysilocarb precursor formulations can generally be made using twotypes of processes, although other processes and variations of thesetypes of processes may be utilized. These processes generally involvecombining precursors to form a polysilocarb precursor formulation. Onetype of process generally involves the mixing together of precursormaterials in preferably a solvent free process with essentially nochemical reactions taking place, e.g., “the mixing process.” The othertype of process generally involves chemical reactions to form specific,e.g., custom, polysilocarb precursor formulations, which could bemonomers, dimers, trimers and polymers. Generally, in the mixing processessentially all, and preferably all, of the chemical reactions takeplace during subsequent processing, such as during curing, pyrolysis andboth. It should be understood that these terms—reaction type process andthe mixing type process—are used for convenience, e.g., a short handreference, and should not be viewed as limiting. Further, it should beunderstood that combinations and variations of these two processes maybe used in reaching a precursor formulation, and in reachingintermediate, end and final products. Depending upon the specificprocess and desired features of the product the precursors and startingmaterials for one process type can be used in the other. These processesprovide great flexibility to create custom features for intermediate,end and final products, and thus, typically, either process type, andcombinations of them, can provide a specific predetermined product. Inselecting which type of process is preferable factors such as cost,controllability, shelf life, scale up, manufacturing ease, etc., can beconsidered.

The two process types are described in this specification, among otherplaces, under their respective headings. It should be understood thatthe teachings for one process, under one heading, and the teachings forthe other process, under the other heading, can be applicable to eachother, as well as, being applicable to other sections and teachings inthis specification, and vice versa. The starting or precursor materialsfor one type of process may be used in the other type of process.Further, it should be understood that the processes described underthese headings should be read in context with the entirely of thisspecification, including the various examples. Thus, the use of headingsin this specification should not limit the scope of protection affordthe present inventions.

Additionally, the formulations from the mixing type process may be usedas a precursor, or component in the reaction type process. Similarly, aformulation from the reaction type process may be used in the mixingtype process. Thus, and preferably, the optimum performance and featuresfrom either process can be combined and utilized to provide a costeffective and efficient process and end product.

In addition to being commercially available the precursors may be madeby way of an alkoxylation type, e.g., ethoxylation process. In thisprocess chlorosilanes are reacted with ethanol in the presences of acatalysis, e.g., HCl, to provide the precursor materials, whichmaterials may further be reacted to provide longer chain precursors.Other alcohols, e.g., Methanol may also be used. Thus, the compounds theformulas of FIGS. 60A to 60F are reacted with ethanol (C—C—OH) to formthe precursors of FIGS. 46-59. In some of these reactions phenols may bethe source of the phenyl group, which is substitute for a hydride groupthat has been placed on the silicon. One, two or more step reaction mayneed to take place.

The Mixing Type Process

Precursor materials may be methyl hydrogen, and substituted and modifiedmethyl hydrogens, siloxane backbone additives, reactive monomers,reaction products of a siloxane backbone additive with a silane modifieror an organic modifier, and other similar types of materials, such assilane based materials, silazane based materials, carbosilane basedmaterials, phenol/formaldehyde based materials, and combinations andvariations of these. The precursors are preferably liquids at roomtemperature, although they may be solids that are melted, or that aresoluble in one of the other precursors. (In this situation, however, itshould be understood that when one precursor dissolves another, it isnevertheless not considered to be a “solvent” as that term is used withrespect to the prior art processes that employ non-constituent solvents,e.g., solvents that do not form a part or component of the end product,are treated as waste products, and both.)

The precursors are mixed together in a vessel, preferably at roomtemperature. Preferably, little, and more preferably no solvents, e.g.,water, organic solvents, polar solvents, non-polar solvents, hexane,THF, toluene, are added to this mixture of precursor materials.Preferably, each precursor material is miscible with the others, e.g.,they can be mixed at any relative amounts, or in any proportions, andwill not separate or precipitate. At this point the “precursor mixture”or “polysilocarb precursor formulation” is compete (noting that if onlya single precursor is used the material would simply be a “polysilocarbprecursor” or a “polysilocarb precursor formulation”). Althoughcomplete, fillers and reinforcers may be added to the formulation. Inpreferred embodiments of the formulation, essentially no, and morepreferably no chemical reactions, e.g., crosslinking or polymerization,takes place within the formulation, when the formulation is mixed, orwhen the formulation is being held in a vessel, on a prepreg, or othertime period, prior to being cured.

Additionally, inhibitors such as cyclohexane, 1-Ethynyl-1-cyclohexanol(which may be obtained from ALDRICH), Octamethylcyclotetrasiloxane,tetramethyltetravinylcyclotetrasiloxane (which may act, depending uponamount and temperature as a reactant or a reactant retardant (i.e.,slows down a reaction to increase pot life), e.g., at room temperatureit is a retardant and at elevated temperatures it is a reactant), may beadded to the polysilocarb precursor formulation, e.g., an inhibitedpolysilocarb precursor formulation. Other materials, as well, may beadded to the polysilocarb precursor formulation, e.g., a filledpolysilocarb precursor formulation, at this point in processing,including fillers such as SiC powder, PDC particles, pigments,particles, nano-tubes, whiskers, or other materials, discussed in thisspecification or otherwise known to the arts. Further, a formulationwith both inhibitors and fillers would be considered an inhibited,filled polysilocarb precursor formulation.

Depending upon the particular precursors and their relative amounts inthe polysilocarb precursor formulation, polysilocarb precursorformulations may have shelf lives at room temperature of greater than 12hours, greater than 1 day, greater than 1 week, greater than 1 month,and for years or more. These precursor formulations may have shelf livesat high temperatures, for example, at about 90° F., of greater than 12hours, greater than 1 day, greater than 1 week, greater than 1 month,and for years or more. The use of inhibitors may further extend theshelf life in time, for higher temperatures, and combinations andvariations of these. As used herein the term “shelf life” should begiven its broadest possible meaning unless specified otherwise, andwould include the formulation being capable of being used for itsintended purpose, or performing, e.g., functioning, for its intendeduse, at 100% percent as well as a freshly made formulation, at leastabout 90% as well as a freshly made formulation, at least about 80% aswell as a freshly made formulation, and at about 70% as well as afreshly made formulation.

Precursors and precursor formulations are preferably non-hazardousmaterials. They have flash points that are preferably above about 70°C., above about 80° C., above about 100° C. and above about 300° C., andabove. They may be noncorrosive. They may have as low vapor pressure,may have low or no odor, and may be non- or mildly irritating to theskin.

A catalyst may be used, and can be added at the time of, prior to,shortly before, or at an earlier time before the precursor formulationis formed or made into a structure, prior to curing. The catalysisassists in, advances, promotes the curing of the precursor formulationto form a preform.

The time period where the precursor formulation remains useful forcuring after the catalysis is added is referred to as “pot life”, e.g.,how long can the catalyzed formulation remain in its holding vesselbefore it should be used. Depending upon the particular formulation,whether an inhibitor is being used, and if so the amount being used,storage conditions, e.g., temperature, and potentially other factors,precursor formulations can have pot lives, for example of from about 5minutes to about 10 days, about 1 day to about 6 days, about 4 to 5days, about 1 hour to about 24 hours, and about 12 hours to about 24hours.

The catalysis can be any platinum (Pt) based catalyst, which can forexample be diluted to a range from: 1 part per million Pt to 200 partsper million (ppm) and preferably in the 5 ppm to 50 ppm range. It can bea peroxide based catalyst with a 10 hour half life above 90 C at aconcentration of between 0.5% and 2%. It can be an organic basedperoxide. It can be any organometallic catalyst capable of reacting withSi—H bond, Si—OH bonds, or unsaturated carbon bonds, these catalyst mayinclude: dibutyltin dilaurate, zinc octoate, and titanium organometalliccompounds. Combinations and variations of these and other catalysts maybe used. Such catalysts may be obtained from ARKEMA under the trade nameLUPEROX, e.g., LUPEROX 231.

Further, custom and specific combinations of these and other catalystsmay be used, such that they are matched to specific formulationformulations, and in this way selectively and specifically catalyze thereaction of specific constituents. Custom and specific combinations ofcatalysts may be used, such that they are matched to specificformulation formulations, and in this way selectively and specificallycatalyze the reaction of specific constituents at specific temperatures.Moreover, the use of these types of matched catalyst—formulationssystems may be used to provide predetermined product features, such asfor example, pore structures, porosity, densities, density profiles, andother morphologies of cured structures and ceramics.

In this mixing type process for making a precursor formulation,preferably chemical reactions or molecular rearrangements only takeplace during the making of the precursors, the curing process of thepreform, and in the pyrolizing process. Thus, chemical reactions, e.g.,polymerizations, reductions, condensations, substitutions, take place orare utilized in the making of a precursor. In making a polysilocarbprecursor formulation preferably no and essentially no, chemicalreactions and molecular rearrangements take place. These embodiments ofthe present mixing type process, which avoid the need to, and do not,utilize a polymerization or other reaction during the making of aprecursor formulation, provides significant advantages over priormethods of making polymer derived ceramics. Preferably, in theembodiments of these mixing type of formulations and processes,polymerization, crosslinking or other chemical reactions take placeprimarily, preferably essentially, and more preferably solely in thepreform during the curing process.

The precursor may be methyl hydrogen (MH), which formula is shown inFIG. 10. The MH may have a molecular weight (mw) may be from about 400mw to about 10,000 mw, from about 600 mw to about 1,000 mw, and may havea viscosity preferably from about 20 cps to about 40 cps. The percentageof methylsiloxane units “X” may be from 1% to 100%. The percentage ofthe dimethylsiloxane units “Y” may be from 0% to 99%. This precursor maybe used to provide the backbone of the cross-linked structures, as wellas, other features and characteristics to the cured preform and ceramicmaterial. Typically, methyl hydrogen fluid (MHF) has minimal amounts of“Y”, and more preferably “Y” is for all practical purposes zero.

The precursor may be a siloxane backbone additive, such as vinylsubstituted polydimethyl siloxane, which formula is shown in FIG. 11.This precursor may have a molecular weight (mw) may be from about 400 mwto about 10,000 mw, and may have a viscosity preferably from about 50cps to about 2,000 cps. The percentage of methylvinylsiloxane units “X”may be from 1% to 100%. The percentage of the dimethylsiloxane units “Y”may be from 0% to 99%. Preferably, X is 100%. This precursor may be usedto decrease cross-link density and improve toughness, as well as, otherfeatures and characteristics to the cured preform and ceramic material.

The precursor may be a siloxane backbone additive, such as vinylsubstituted and vinyl terminated polydimethyl siloxane, which formula isshown in FIG. 12. This precursor may have a molecular weight (mw) may befrom about 500 mw to about 15,000 mw, and may preferably have amolecular weight from about 500 mw to 1,000 mw, and may have a viscositypreferably from about 10 cps to about 200 cps. The percentage ofmethylvinylsiloxane units “X” may be from 1% to 100%. The percentage ofthe dimethylsiloxane units “Y” may be from 0% to 99%. This precursor maybe used to provide branching and decrease the cure temperature, as wellas, other features and characteristics to the cured preform and ceramicmaterial.

The precursor may be a siloxane backbone additive, such as vinylsubstituted and hydrogen terminated polydimethyl siloxane, which formulais shown in FIG. 13. This precursor may have a molecular weight (mw) maybe from about 300 mw to about 10,000 mw, and may preferably have amolecular weight from about 400 mw to 800 mw, and may have a viscositypreferably from about 20 cps to about 300 cps. The percentage ofmethylvinylsiloxane units “X” may be from 1% to 100%. The percentage ofthe dimethylsiloxane units “Y” may be from 0% to 99%. This precursor maybe used to provide branching and decrease the cure temperature, as wellas, other features and characteristics to the cured preform and ceramicmaterial.

The precursor may be a siloxane backbone additive, such as allylterminated polydimethyl siloxane, which formula is shown in FIG. 14.This precursor may have a molecular weight (mw) may be from about 400 mwto about 10,000 mw, and may have a viscosity preferably from about 40cps to about 400 cps. The repeating units are the same. This precursormay be used to provide UV curability and to extend the polymeric chain,as well as, other features and characteristics to the cured preform andceramic material.

The precursor may be a siloxane backbone additive, such as vinylterminated polydimethyl siloxane, which formula is shown in FIG. 15.This precursor may have a molecular weight (mw) may be from about 200 mwto about 5,000 mw, and may preferably have a molecular weight from about400 mw to 1,500 mw, and may have a viscosity preferably from about 10cps to about 400 cps. The repeating units are the same. This precursormay be used to provide a polymeric chain extender, improve toughness andto lower cure temperature down to for example room temperature curing,as well as, other features and characteristics to the cured preform andceramic material.

The precursor may be a siloxane backbone additive, such as silanol(hydroxy) terminated polydimethyl siloxane, which formula is shown inFIG. 16. This precursor may have a molecular weight (mw) may be fromabout 400 mw to about 10,000 mw, and may preferably have a molecularweight from about 600 mw to 1,000 mw, and may have a viscositypreferably from about 30 cps to about 400 cps. The repeating units arethe same. This precursor may be used to provide a polymeric chainextender, a toughening mechanism, can generate nano- and micro-scaleporosity, and allows curing at room temperature, as well as otherfeatures and characteristics to the cured preform and ceramic material.

The precursor may be a siloxane backbone additive, such as silanol(hydroxy) terminated vinyl substituted dimethyl siloxane, which formulais shown in FIG. 18. This precursor may have a molecular weight (mw) maybe from about 400 mw to about 10,000 mw, and may preferably have amolecular weight from about 600 mw to 1,000 mw, and may have a viscositypreferably from about 30 cps to about 400 cps. The percentage ofmethylvinylsiloxane units “X” may be from 1% to 100%. The percentage ofthe dimethylsiloxane units “Y” may be from 0% to 99%.

The precursor may be a siloxane backbone additive, such as hydrogen(hydride) terminated polydimethyl siloxane, which formula is shown inFIG. 17. This precursor may have a molecular weight (mw) may be fromabout 200 mw to about 10,000 mw, and may preferably have a molecularweight from about 500 mw to 1,500 mw, and may have a viscositypreferably from about 20 cps to about 400 cps. The repeating units arethe same. This precursor may be used to provide a polymeric chainextender, as a toughening agent, and it allows lower temperature curing,e.g., room temperature, as well as, other features and characteristicsto the cured preform and ceramic material.

The precursor may be a siloxane backbone additive, such as phenylterminated polydimethyl siloxane, which formula is shown in FIG. 19.This precursor may have a molecular weight (mw) may be from about 500 mwto about 2,000 mw, and may have a viscosity preferably from about 80 cpsto about 300 cps. The repeating units are the same. This precursor maybe used to provide a toughening agent, and to adjust the refractiveindex of the polymer to match the refractive index of various types ofglass, to provide for example transparent fiberglass, as well as, otherfeatures and characteristics to the cured preform and ceramic material.

The precursor may be a siloxane backbone additive, such as methyl-phenylterminated polydimethyl siloxane, which formula is shown in 20. Thisprecursor may have a molecular weight (mw) may be from about 500 mw toabout 2,000 mw, and may have a viscosity preferably from about 80 cps toabout 300 cps. The repeating units are the same. This precursor may beused to provide a toughening agent and to adjust the refractive index ofthe polymer to match the refractive index of various types of glass, toprovide for example transparent fiberglass, as well as, other featuresand characteristics to the cured preform and ceramic material.

The precursor may be a siloxane backbone additive, such as diphenyldimethyl polysiloxane, which formula is shown in FIG. 21. This precursormay have a molecular weight (mw) may be from about 500 mw to about20,000 mw, and may have a molecular weight from about 800 to about4,000, and may have a viscosity preferably from about 100 cps to about800 cps. The percentage of dimethylsiloxane units “X” may be from 25% to95%. The percentage of the diphenyl siloxane units “Y” may be from 5% to75%. This precursor may be used to provide similar characteristics tothe precursor of FIG. 20, as well as, other features and characteristicsto the cured preform and ceramic material.

The precursor may be a siloxane backbone additive, such as vinylterminated diphenyl dimethyl polysiloxane, which formula is shown inFIG. 22. This precursor may have a molecular weight (mw) may be fromabout 400 mw to about 20,000 mw, and may have a molecular weight fromabout 800 to about 2,000, and may have a viscosity preferably from about80 cps to about 600 cps. The percentage of dimethylsiloxane units “X”may be from 25% to 95%. The percentage of the diphenyl siloxane units“Y” may be from 5% to 75%. This precursor may be used to provide chainextension, toughening agent, changed or altered refractive index, andimprovements to high temperature thermal stability of the curedmaterial, as well as, other features and characteristics to the curedpreform and ceramic material.

The precursor may be a siloxane backbone additive, such as hydroxyterminated diphenyl dimethyl polysiloxane, which formula is shown inFIG. 23. This precursor may have a molecular weight (mw) may be fromabout 400 mw to about 20,000 mw, and may have a molecular weight fromabout 800 to about 2,000, and may have a viscosity preferably from about80 cps to about 400 cps. The percentage of dimethylsiloxane units “X”may be from 25% to 95%. The percentage of the diphenyl siloxane units“Y” may be from 5% to 75%. This precursor may be used to provide chainextension, toughening agent, changed or altered refractive index, andimprovements to high temperature thermal stability of the curedmaterial, can generate nano- and micro-scale porosity, as well as otherfeatures and characteristics to the cured preform and ceramic material.

The precursor may be a siloxane backbone additive, such as hydrideterminated diphenyl dimethyl polysiloxane, which formula is shown inFIG. 24. This precursor may have a molecular weight (mw) may be fromabout 400 mw to about 20,000 mw, and may have a molecular weight fromabout 800 to about 2,000, and may have a viscosity preferably from about60 cps to about 300 cps. The percentage of dimethylsiloxane units “X”may be from 25% to 95%. The percentage of the diphenyl siloxane units“Y” may be from 5% to 75%. This precursor may be used to provide chainextension, toughening agent, changed or altered refractive index, andimprovements to high temperature thermal stability of the curedmaterial, as well as, other features and characteristics to the curedpreform and ceramic material.

The precursor may be a siloxane backbone additive, such as styrene vinylbenzene dimethyl polysiloxane, which formula is shown in FIG. 25. Thisprecursor may have a molecular weight (mw) may be from about 800 mw toat least about 10,000 mw to at least about 20,000 mw, and may have aviscosity preferably from about 50 cps to about 350 cps. The percentageof styrene vinyl benzene siloxane units “X” may be from 1% to 60%. Thepercentage of the dimethylsiloxane units “Y” may be from 40% to 99%.This precursor may be used to provide improved toughness, decreasesreaction cure exotherm, may change or alter the refractive index, adjustthe refractive index of the polymer to match the refractive index ofvarious types of glass, to provide for example transparent fiberglass,as well as, other features and characteristics to the cured preform andceramic material.

The precursor may be a reactive monomer, such astetramethyltetravinylcyclotetrasiloxane (“TV”), which formula is shownin FIG. 26. This precursor may be used to provide a branching agent, athree-dimensional cross-linking agent, (and in certain formulations,e.g., above 2%, and certain temperatures (e.g., about from about roomtemperature to about 60° C., it acts as an inhibitor to cross-linking,e.g., in may inhibit the cross-linking of hydride and vinyl groups), aswell as, other features and characteristics to the cured preform andceramic material.

The precursor may be a reactive monomer, such as trivinylcyclotetrasiloxane, which formula is shown in FIG. 27. The precursor maybe a reactive monomer, such as divinyl cyclotetrasiloxane, which formulais shown in FIG. 28. The precursor may be a reactive monomer, such asmonohydride cyclotetrasiloxane, which formula is shown in FIG. 29. Theprecursor may be a reactive monomer, such as dihydridecyclotetrasiloxane, which formula is shown in FIG. 30. The precursor maybe a reactive monomer, such as hexamethyl cyclotetrasiloxane, whichformula is shown in FIG. 31 and FIG. 32.

The precursor may be a silane modifier, such as vinyl phenyl methylsilane, which formula is shown in FIG. 33. The precursor may be a silanemodifier, such as diphenyl silane, which formula is shown in FIG. 34.The precursor may be a silane modifier, such as diphenyl methyl silane,which formula is shown in FIG. 35 (which may be used as an end capper orend termination group). The precursor may be a silane modifier, such asphenyl methyl silane, which formula is shown in FIG. 36 (which may beused as an end capper or end termination group).

The precursors of FIGS. 33, 34 and 36 can provide chain extenders andbranching agents. They also improve toughness, alter refractive index,and improve high temperature cure stability of the cured material, aswell as improving the strength of the cured material, among otherthings. The precursor of FIG. 35 may function as an end capping agent,that may also improve toughness, alter refractive index, and improvehigh temperature cure stability of the cured material, as well asimproving the strength of the cured material, among other things.

The precursor may be a reaction product of a silane modifier with asiloxane backbone additive, such as phenyl methyl silane substituted MH,which formula is shown in FIG. 35.

The precursor may be a reaction product of a silane modifier (e.g.,FIGS. 33 to 36) with a vinyl terminated siloxane backbone additive(e.g., FIG. 15), which formula is shown in FIG. 38, where R may be thesilane modifiers having the structures of FIGS. 33 to 36.

The precursor may be a reaction product of a silane modifier (e.g.,FIGS. 33 to 36) with a hydroxy terminated siloxane backbone additive(e.g., FIG. 16), which formula is shown in FIG. 39, where R may be thesilane modifiers having the structures of FIGS. 33 to 36.

The precursor may be a reaction product of a silane modifier (e.g.,FIGS. 33 to 36) with a hydride terminated siloxane backbone additive(e.g., FIG. 17), which formula is shown in FIG. 40, where R may be thesilane modifiers having the structures of FIGS. 33 to 36.

The precursor may be a reaction product of a silane modifier (e.g.,FIGS. 33 to 36) with TV (e.g., FIG. 26), which formaula is shown in FIG.39.

The precursor may be a reaction product of a silane modifier (e.g.,FIGS. 33 to 36) with a cyclosiloxane, examples of which formulas areshown in FIG. 26 (TV), FIG. 41, and in FIG. 42, where R₁, R₂, R₃, and R₄may be a methyl or the silane modifiers having the structures of FIGS.33 to 36, taking into consideration steric hindrances.

The precursor may be a partially hydrolyzed tertraethyl orthosilicate,which formula is shown in FIG. 44, such as TES 40 or Silbond 40.

The precursor may also be a methylsesquisilioxane such as SR-350available from General Electric Company, Wilton, Conn. The precursor mayalso be a phenyl methyl siloxane such as 604 from Wacker Chemie AG. Theprecursor may also be a methylphenylvinylsiloxane, such as H62 C fromWacker Chemie AG.

The precursors may also be selected from the following: SiSiB® HF2020,TRIMETHYLSILYL TERMINATED METHYL HYDROGEN SILICONE FLUID 63148-57-2;SiSiB® HF2050 TRIMETHYLSILYL TERMINATED METHYLHYDROSILOXANEDIMETHYLSILOXANE COPOLYMER 68037-59-2; SiSiB® HF2060 HYDRIDE TERMINATEDMETHYLHYDROSILOXANE DIMETHYLSILOXANE COPOLYMER 69013-23-6; SiSiB® HF2038HYDROGEN TERMINATED POLYDIPHENYL SILOXANE; SiSiB® HF2068 HYDRIDETERMINATED METHYLHYDROSILOXANE DIMETHYLSILOXANE COPOLYMER 115487-49-5;SiSiB® HF2078 HYDRIDE TERMINATED POLY(PHENYLDIMETHYLSILOXY) SILOXANEPHENYL SILSESQUIOXANE, HYDROGEN-TERMINATED 68952-30-7; SiSiB® VF6060VINYLDIMETHYL TERMINATED VINYLMETHYL DIMETHYL POLYSILOXANE COPOLYMERS68083-18-1; SiSiB® VF6862 VINYLDIMETHYL TERMINATED DIMETHYL DIPHENYLPOLYSILOXANE COPOLYMER 68951-96-2; SiSiB® VF6872 VINYLDIMETHYLTERMINATED DIMETHYL-METHYLVINYL-DIPHENYL POLYSILOXANE COPOLYMER; SiSiB®PC9401 1,1,3,3-TETRAMETHYL-1,3-DIVINYLDISILOXANE 2627-95-4; SiSiB®PF1070 SILANOL TERMINATED POLYDIMETHYLSILOXANE (OF1070) 70131-67-8;SiSiB@ OF1070 SILANOL TERMINATED POLYDIMETHYSILOXANE 70131-67-8;OH-ENDCAPPED POLYDIMETHYLSILOXANE HYDROXY TERMINATED OLYDIMETHYLSILOXANE73138-87-1; SiSiB® VF6030 VINYL TERMINATED POLYDIMETHYL SILOXANE68083-19-2; and, SiSiB® HF2030 HYDROGEN TERMINATED POLYDIMETHYLSILOXANEFLUID 70900-21-9.

Thus, in additional to the forgoing specific precursors, it iscontemplated that a precursor may be compound of the general formula ofFIG. 43, wherein end cappers E₁ and E₂ are chosen from groups such astrimethyl silicon (SiC₃H₉) FIG. 43A, dimethyl silicon hydroxy (SiC₂OH₇)FIG. 43C, dimethyl silicon hydride (SiC₂H₇) FIG. 43B and dimethyl vinylsilicon (SiC₄H₉) FIG. 43D. The R groups R₁, R₂, R₃, and R₄ may all bedifferent, or one or more may be the same, thus R2 is the same as R3 isthe same as R₄, R₁ and R2 are different with R₃ and R₄ being the same,etc. The R groups are chosen from groups such as phenyl, vinyl, hydride,methyl, ethyl, allyl, phenylethyl, methoxy, and alkoxy.

In general, embodiments of formulations for polysilocarb formulationsmay for example have from about 20% to about 99% MH, about 0% to about30% siloxane backbone additives, about 1% to about 60% reactivemonomers, and, about 0% to about 90% reaction products of a siloxanebackbone additives with a silane modifier or an organic modifierreaction products.

In mixing the formulations a sufficient time to permit the precursors tobecome effectively mixed and dispersed. Generally, mixing of about 15minutes to an hour is sufficient. Typically, the precursor formulationsare relatively, and essentially, shear insensitive, and thus the type ofpumps or mixing are not critical. It is further noted that in higherviscosity formulations additional mixing time may be required. Thetemperature of the formulations, during mixing should be kept belowabout 45 degrees C., and preferably about 10 degrees C. (It is notedthat these mixing conditions are for the pre-catalyzed formulations)

The Reaction Type Process

In the reaction type process, in general, a chemical reaction is used tocombine one, two or more precursors, typically in the presence of asolvent, to form a precursor formulation that is essentially made up ofa single polymer that can then be cured and if need be pyrolized. Thisprocess provides the ability to build custom precursor formulations thatwhen cured can provide plastics having unique and desirable featuressuch as high temperature, flame resistance and retardation, strength andother features. The cured materials can also be pyrolized to formceramics having unique features. The reaction type process allows forthe predetermined balancing of different types of functionality in theend product by selecting function groups for incorporation into thepolymer that makes up the precursor formulation, e.g., phenyls whichtypically are not used for ceramics but have benefits for providing hightemperature capabilities for plastics, and styrene which typically doesnot provide high temperature features for plastics but provides benefitsfor ceramics.

In general a custom polymer for use as a precursor formulation is madeby reacting precursors in a condensation reaction to form the polymerprecursor formulation. This precursor formulation is then cured into apreform through a hydrolysis reaction. The condensation reaction forms apolymer of the type shown in FIG. 45, where R₁ and R₂ in the polymericunits can be a H, a Methyl (Me)(—C), a vinyl (—C═C), alkyl (—R), aphenyl (Ph)(—C₆H₅), an ethoxy (—O—C—C), a siloxy, methoxy (—O—C),alkoxy, (—O—R), hydroxy, (—O—H), and phenylethyll (—C—C—C₆H₅). R₁ and R₂may be the same or different. The custom precursor polymers can haveseveral different polymeric units, e.g., A₁, A₂, A_(n), and may includeas many as 10, 20 or more units, or it may contain only a single unit.(For example, if methyl hydrogen fluid is made by the reaction process).The end units, Si End 1 and Si End 2, can come from the precursors ofFIGS. 50, 52, 57, and 49. Additionally, if the polymerization process isproperly controlled a hydroxy end cap can be obtained from theprecursors used to provide the repeating units of the polymer.

In general, the precursors, e.g., FIGS. 46 to 59 are added to a vesselwith ethanol (or other material to absorb heat, e.g., to provide thermalmass), an excess of water, and hydrochloric acid (or other protonsource). This mixture is heated until it reaches its activation energy,after which the reaction is exothermic. In this reaction the waterreacts with an ethoxy group of the silicon of the precursor monomer,forming a hydroxy (with ethanol as the byproduct). Once formed thishydroxy becomes subject to reaction with an ethoxy group on the siliconof another precursor monomer, resulting in a polymerization reaction.This polymerization reaction is continued until the desired chainlength(s) is built.

Control factors for determining chain length are: the monomers chosen(generally, the smaller the monomers the more that can be added beforethey begin to coil around and bond to themselves); the amount and pointin the reaction where end cappers are introduced; and the amount ofwater and the rate of addition. Thus, the chain lengths can be fromabout 180 mw (viscosity about 5 cps) to about 65,000 mw (viscosity ofabout 10,000 cps), greater than about 1000 mw, greater than about 10,000mw, greater than about 50,000 mw and greater. Further, the polymerizedprecursor formulation may, and typically does, have polymers ofdifferent molecular weights, which can be predetermined to provideformulation, cured, and ceramic product performance features.

Upon completion of the polymerization reaction the material istransferred into a separation apparatus, e.g., a separation funnel,which has an amount of deionized water that is from about 1.2× to about1.5× the mass of the material. This mixture is vigorously stirred forabout less than 1 minute and preferably from about 5 to 30 sections.Once stirred the material is allowed to settle and separate, which maytake from about 1 to 2 hours. The polymer is the higher density materialand is removed from the vessel. This removed polymer is then dried byeither warming in a shallow tray at 90 C for about two hours; or,preferably, is passed through a wiped film distillation apparatus, toremove any residual water and ethanol. Alternatively, sodium bicarbonatesufficient to buffer the aqueous layer to a pH of about 4 to about 7 isadded. It is further understood that other, and commercial, manners ofseparating the polymer from the material may be employed.

Preferably a catalyst is used in the curing process of the polymerpressure formulations from the reaction type process. The same polymersas used for curing the formulation from the mixing type process can beused. It is noted that unlike the mixing type formulations, a catalystis not necessarily required. However, if not used, reaction time andrates will be slower. The pyrolysis of the cured material is essentiallythe same as the cured material from the mixing process.

Curing and Pyrolysis

The preform can be cured in a controlled atmosphere, such as an inertgas, or it can be cured in the atmosphere. The curing can be conductedin reduce pressure, e.g., vacuum, or in reduced pressure flowing gas(e.g., inert) streams. The cure conditions, e.g., temperature, time,rate, can be predetermined by the formulation to match, for example thesize of the preform, the shape of the preform, or the mold holding thepreform to prevent stress cracking, off gassing, or other problemsassociated with the curing process. Further, the curing conditions maybe such as to take advantage of, in a controlled manner, what may havebeen previously perceived as problems associated with the curingprocess. Thus, for example, off gassing may be used to create a foammaterial having either open or closed structure. Further, the porosityof the material may be predetermined such that, for example, aparticular pore size may be obtained, and in this manner a filter orceramic screen having predetermined pore sizes, flow characteristic maybe made.

The preforms, either unreinforced, neat, or reinforced, may be used as astand alone product, an end product, a final product, or a preliminaryproduct for which later machining or processing may be performed on. Thepreforms may also be subject to pyrolysis, which converts the preformmaterial into a ceramic.

During the curing process some formulations may exhibit an exotherm,i.e., a self heating reaction, that can produce a small amount of heatto assist or drive the curing reaction, or they may produce a largeamount of heat that may need to be managed and removed in order to avoidproblems, such as stress fractures. During the cure off gassingtypically occurs and results in a loss of material, which loss isdefined generally by the amount of material remaining, e.g., cure yield.The formulations and polysilocarb precursor formulations of embodimentsof the present inventions can have cure yields of at least about 90%,about 92%, about 100%. In fact, with air cures the materials may havecure yields above 100%, e.g., about 101-105%, as a result of oxygenbeing absorbed from the air. Additionally, during curing the materialshrinks, this shrinkage may be, depending upon the formulation and thenature of the preform shape, and whether the preform is reinforce, neator unreinforced, from about 20%, less than 20%, less than about 15%,less than about 5%, less than about 1%, less than about 0.5%, less thanabout 0.25% and smaller.

In pyrolizing the preform, or cured structure or cured material, it isheated to above about 650° C. to about 1,200° C. At these temperaturestypically all organic structures are either removed or combined with theinorganic constituents to form a ceramic. Typically at temperatures inthe 650° C. to 1,200° C. range the material is an amorphous glassyceramic. When heated above 1,200° C. the material may from nanocrystalline structures, or micro crystalline structures, such as SiC,Si3N₄, SiCN, β SiC, and above 1,900° C. an α SiC structure may form.

During pyrolysis material is loss through off gassing. The amount ofmaterial remaining at the end of a pyrolysis set is referred to as charyield (or pyrolysis yield). The formulations and polysilocarb precursorformulations of embodiments of the present inventions can have charyields of at least about 60%, about 70%, about 80%, and at least about90%, at least about 91% and greater. In fact, with air pyrolysis thematerials may have cure yields well above 91%, which can approach 100%.In order to avoid the degradation of the material in an air pyrolysis(noting that typically pyrolysis is conducted in an inert atmospheres)specifically tailored formulations must be used, such as for example,formulations high in phenyl content (at least about 11%, and preferablyat least about 20% by weight phenyls), formulations high in allylcontent (at least about 15% to about 60%). Thus, there is providedformulations and polysilocarb precursor formulations that are capable ofbeing air pyrolized to form a ceramic and to preferably do so at charyield in excess of at least about 80% and above 88%.

The initial or first pyrolysis step generally yields a structure that isnot very dense, and for example, has not reached the density requiredfor its intended use. However, in some examples, such as the use oflight weight spheres, the first pyrolysis may be sufficient. Thus,typically a reinfiltration process may be performed on the pyrolizedmaterial, to add in additional polysilocarb precursor formulationmaterial, to fill in, or fill the voids and spaces in the structure.This reinfiltrated material is they repyrolized. This process ofpyrolization, reinfiltration may be repeated, through one, two, three,and up to 10 or more times to obtain the desired density of the finalproduct. Additionally, with formulations of embodiments of the presentinventions, the viscosity of the formulation may be tailored to providemore efficient reinfiltrations, and thus, a different formulation may beused at later reinfiltration steps, as the voids or pores become smallerand more difficult to get the formulation material into it. The highchar yields, and other features of embodiments of the present invention,enable the manufacture of completely closed structures, e.g., “heliumtight” materials, with less than twelve reinfiltration steps, less thanabout 10 reinfiltrations steps and less than five reinfiltrations steps.Thus, by way of example, an initial inert gas pyrolysis may be performedwith a high char yield formulation followed by four reinfiltration airpyrolysis steps.

Upon curing the polysilocarb precursor formulation a cross linkingreaction takes place that provides a cross linked structure having,among other things, an —R₁—Si—C—C—Si—O—Si—C—C—Si—R₂— where R₁ and R₂vary depending upon, and are based upon, the precursors used in theformulation.

Embodiments of the present inventions have the ability to utilizeprecursors that have impurities, high-level impurities and significantimpurities. Thus, the precursors may have more than about 0.1%impurities, more than about 0.5%, more than about 1% impurities, morethan about 5% impurities, more than about 10% impurities, and more thanabout 50% impurities. In using materials with impurities, the amounts ofthese impurities, or at least the relative amounts, so that the amountof actual precursor is known, should preferably be determined by forexample GPC (Gel Permeation Chromatography) or other methods ofanalysis. In this manner the formulation of the polysilocarb precursorformulation may be adjusted for the amount of impurities present. Theability of embodiments of the present invention to utilize lower levelimpurity materials, and essentially impure materials, and highly impurematerials, provides significant advantages over other method of makingpolymer derived ceramics. This provides two significant advantages,among other things. First, the ability to use impure, lower purity,materials in embodiments of the present inventions, provides the abilityto greatly reduce the cost of the formulations and end products, e.g.,cured preforms, cured parts, and ceramic parts or structures. Second,the ability to use impure, lower purity, materials in embodiments of thepresent inventions, provides the ability to have end products, e.g.,cured preforms, cured parts, and ceramic parts or structures, that havea substantially greater consistence from part to part, becausevariations in starting materials can be adjusted for during theformulation of each polysilocarb precursor formulation.

Turning to FIG. 61 there is provided an embodiment of a proppant preformforming and curing system 6100. The system 6100 has a curing tower 6101,a tank 6119 for holding the polysiloxane precursor batch, a meteringdevice 6118 for transferring the batch along feed line 6117 to adistribution header 6103. Mixing, agitating, commingling, pumping, flowcontrol, reactor, and regulating devices may also be utilized intransferring, handling and metering of the precursor batch. Thedistribution header 6103 has nozzle assemblies 6104, 6105, 6106, 6107,6108, 6109 having nozzles 6104 a, 6105 a, 6106 a, 6107 a, 6108 a, 6109 arespectively. Heat shields 6110, 6111, 6112 protect the nozzleassemblies and distribution header from being damaged by the heat of thetower 6101, or from overheating or otherwise adversely affecting thetemperature of the nozzle assemblies and distribution header. Forexample, they prevent the temperature to rise to the point where thebatch would cure in the distribution header or nozzle assembly thusclogging them. The heat shields may utilize air, such as with an airknife, metallic, ceramic, gas, oil, fluid, chemical, heat exchangers,reflectors, water, and others.

The tower 6101 has wall 6102 containing heating units, as well as,insolation and control devices for the heating units. In the embodimentof FIG. 61 the tower is configured to have two zones: a first or formingzone 6113; and a second or curing zone 6114. Depending upon the size ofthe beads, balls or spherical being formed the forming zone 6113 shouldhave sufficient height, and a temperature selected for that height, thatallows the drops of precursor material leaving a nozzle to form apredetermined shape, for example, as perfect a sphere as is possible,before or when the drop transitions (e.g., falls from zone 6113 to zone6114) into curing zone 6114. Curing zone 6114 should have sufficientheight, and a temperature selected for that height, to cure the preformproppants into hard enough structures that their striking the diverter6115 and being collected and held in the pan 6116 does not adverselyaffect their shape. Additional curing, e.g., a hard cure can take placein the pan 6116, in another furnace, or in a third zone in the tower.

Although two temperature zones and six nozzles are utilized in theembodiment of FIG. 61, more or less zones and nozzles may be used. Thus,there may be a single zone or nozzle, two zones or nozzles, a dozenzones or nozzles, or more, and combinations and variations of these. Ifis further understood that in addition to nozzles these types of devicesmay be used at the top of the tower to initially form or shape the dropof precursor material that becomes the preform proppant. Thus,filaments, vibrating filaments that drip the precursor at a controlledrate and under controlled conditions may be used, as well as, variousspraying, dispensing, and forming techniques. Other apparatus may alsobe employed to form the precursor batch into a spherical type structureand then cure that structure with minimal or no adverse consequences tothe shape of the preform.

The following examples are provided to illustrate various embodiments ofoil field treatments, hydraulic fracturing treatments, processes,precursors, batches, cured preform proppants, synthetic proppants, PDCproppants, and PsDC proppants of the present inventions. These examplesare for illustrative purposes, and should not be viewed as, and do nototherwise limit the scope of the present inventions. The percentagesused in the examples, unless specified otherwise, are weight percents ofthe total batch, preform or structure.

EXAMPLES Example 1

Using a tower forming and cure system, a polysilocarb batch having 75%MH, 15% TV, 10% VT and 1% catalyst (10 ppm platinum and 0.5% Luprox 231peroxide) is formed from a sonic nozzle having an internal diameter of0.180 inches into droplets that fall from the nozzle into and through an8 foot curing tower. The temperature at the top of the tower is from495-505° C. the temperature at the bottom of the tower is 650° C. Thereare no discrete temperature zones in the tower. Airflow up the tower isby convection. A collection pan at the bottom of the tower is maintainedat 110° C. The forming and curing are done in air. The preform proppantsare removed from the pan and post (hard) cured at 200° C. in air for 2hours. The hard cured preform proppants are pyrolized at 1000° C. in anargon atmosphere for 2 hours. The cure yield is from 99% to 101%. Thechar yield is 86%.

Example 2

Using a tower forming and cure system, a polysilocarb batch having 70%MH, 20% TV, 10% VT and 1% catalyst (10 ppm platinum and 0.5% Luprox 231peroxide) is formed from a sonic nozzle having an internal diameter of0.180 inches into droplets that fall from the nozzle into and through an8 foot curing tower. The temperature at the top of the tower is from495-505° C. the temperature at the bottom of the tower is 650° C. Thereare no discrete temperature zones in the tower. Airflow up the tower isby convection. A collection pan at the bottom of the tower is maintainedat 110° C. The forming and curing are done in air. The preform proppantsare removed from the pan and post (hard) cured at 200° C. in air for 2hours. The hard cured preform proppants are pyrolized at 1000° C. in anargon atmosphere for 2 hours. The cure yield is from 99% to 101%. Thechar yield is 86%.

Example 2a

Turning to FIG. 66, there is provided a chart comparing the strength anddensity of an embodiment of the proppant of Example 2 with prior artproppants.

Example 2b

Turning to FIG. 67, there is provided a chart comparing the setting rateof an embodiment of the proppant of Example 2 with prior art proppants.The lower the settling rate the greater the likelihood that the proppantwill remain suspended in the fracturing fluid and travel out furtheraway from the borehole, and into the fracture area, during the fracturetreatment.

Example 2c

Turning to FIG. 68, there is provided a chart comparing the very narrowparticle size distribution of an embodiment of Example 2 with prior artproppants; illustrating the significantly narrower distribution than isfound in the prior art.

Example 3

Using a tower forming and cure system, a polysilocarb batch having 70%MH, 20% TV, 10% VT and 1% catalyst (10 ppm platinum and 0.5% Luprox 231peroxide) is formed from a sonic nozzle having an internal diameter of0.180 inches into droplets that fall from the nozzle into and through an8 foot curing tower. The temperature at the top of the tower is from345° C. the temperature at the bottom of the tower is 550° C. There areno discrete temperature zones in the tower. Airflow up the tower is byconvection. The collection pan is maintained at 110° C. The forming andcuring are done in air. The preform proppants are removed from the panand post (hard) cured at 200° C. in air for 3 hours. The hard curedpreform proppants are pyrolized at 1000° C. in an argon atmosphere for 2hours. The cure yield is from 99% to 101%. The char yield is 86%.

Example 4

PsDC proppants are made using a tower cure system. 50% by volume fly ashis added to a polysilocarb batch having 70% MH, 20% TV, 10% VT and 1%catalyst (10 ppm platinum and 0.5% Luprox 231 peroxide). This batch isformed from a sonic nozzle having an internal diameter of 0.180 inchesinto droplets that fall from the nozzle into and through an 18 footcuring tower. The temperature at the top of the tower is from 200-500°C. the temperature at the bottom of the tower is from 200-600° C. Thereare no discrete temperature zones in the tower. Airflow up the tower isby convection. The collection pan is maintained at 110° C. The formingand curing are done in air. The preform proppants are removed from thepan and post (hard) cured at 200° C. in air for 3 hours. The hard curedpreform proppants are pyrolized at 1000° C. in an argon atmosphere for 2hours. The cure yield is from 99% to 101%. The char yield is 86%.

Example 5

40% by volume AL₂O₃ having a diameter of 0.5 μm is added to apolysilocarb batch having 70% MH, 20% TV, 10% VT and 1% catalyst (10 ppmplatinum and 0.5% Luprox 231 peroxide). Using a tower cure system, thisbatch is formed from a sonic nozzle having an internal diameter of 0.180inches into droplets that fall from the nozzle into and through an 18foot curing tower. The temperature at the top of the tower is from200-500° C. the temperature at the bottom of the tower is from 200-600°C. There are no discrete temperature zones in the tower. Airflow up thetower is by convection. The collection pan is maintained at 110° C. Theforming and curing are done in air. The preform proppants are removedfrom the pan and post (hard) cured at 200° C. in air for 3 hours. Thehard cured preform proppants are pyrolized at 1000° C. in an argonatmosphere for 2 hours. The cure yield is from 99% to 101%. The charyield is 86%.

Example 6

A polysilocarb batch having 70% of the MH precursor (molecular weight ofabout 800) and 30% of the TV precursor are mixed together in a vesseland put in storage for later use. The polysilocarb batch has good shelflife and room temperature and the precursors have not, and do not reactwith each other. The polysilocarb batch has a viscosity of about 15 cps.28% of an about 80 micron to about 325 mesh SiC filler is added to thebatch to make a filled polysilocarb batch, which can be kept for lateruse. Just prior to forming and curing 10 ppm of a platinum catalyst isadded to each of the polysilocarb batches and this catalyzed batch isdropped on a tray to form droplets which are cured in an air oven atabout 125° C. for about 30 minutes. The cured drop structures arespherical type structures with densities of about 1.1-1.7 g/cc,diameters of about 200 microns to about 2 mm, and crush strengths ofabout 3-7 ksi.

Example 7

A polysilocarb batch having 70% of the MH precursor (molecular weight ofabout 800) and 30% of the TV precursor are mixed together in a vesseland put in storage for later use. The polysilocarb batch has good shelflife and room temperature and the precursors have not, and do not reactwith each other. The polysilocarb batch has a viscosity of about 15 cps.21% of a silica fume (about 325 mesh) are added to the batch to make afilled polysilocarb batch, which can be kept for later use. Just priorto forming into preform proppants, 10 ppm of a platinum catalyst isadded to the polysilocarb batch and these catalyzed batches are droppedinto the curing tower and air cured. The cured drop structures arespherical type structures with densities of about 1.1-1.7 g/cc,diameters of about 200 microns, and (API/ISO) crush strengths of about 7k psi.

Example 8

A polysilocarb batch having 75% of the MH precursor (molecular weight ofabout 800) and 25% of the TV precursor are mixed together in a vesseland put in storage for later use. The polysilocarb batch has good shelflife and room temperature and the precursors have not, and do not reactwith each other. The polysilocarb batch has a viscosity of about 18 cps.40% of a silica fume to about 325 mesh silica filler is added to thebatch to make a filled polysilocarb batch, which can be kept for lateruse. Prior to forming and curing 10 ppm of a platinum catalyst is addedto each of the polysilocarb batch and this batch is formed intospherical proppants under similar forming and curing conditions to thoseof the forming and curing tower in Example 1.

Example 9

A polysilocarb batch having 10% of the MH precursor (molecular weight ofabout 800), 73% of the STY (FIG. 10 and having 10% X, molecular weightof about 1,000), and 16% of the TV precursor, and 1% of the OHterminated precursor of the formula of FIG. 5, having a molecular weightof about 1,000 are mixed together in a vessel and put in storage forlater use. The polysilocarb batch has good shelf life and roomtemperature and the precursors have not, and do not react with eachother. The polysilocarb batch has a viscosity of about 72 cps. 10 ppm ofa platinum catalyst is added to the polysilocarb batch. Drops of thecatalyzed batch are dripped into a hot air column having a temperatureof about 375° C. and fall by gravity for about a distance of 8 ft in theair column. The cured spheres from the bottom of the air column arepyrolized in an inert atmosphere at 1,000° C. for about 120 minutes. Thepyrolized round spheres have a very uniform size (e.g., monosizedistribution), density of about 1.9-2.0 g/cc, a diameter of about400-800 microns, and a (API/ISO) crush strength of about 5.5-7 k psi.

Example 10

A polysilocarb batch having about 70% MH, 20% TV precursor, 10% VT(molecular weight of about 6000), and 1% of the OH terminated precursorof the formula of FIG. 16, having a molecular weight of about 800 aremixed together in a vessel and put in storage for later use. Thepolysilocarb batch has good shelf life and room temperature and theprecursors have not, and do not react with each other. The polysilocarbbatch has a viscosity of about 55 cps. Prior to forming the preformproppants 10 ppm of a platinum and peroxide catalyst mixture is added tothe polysilocarb batch. Drops of the catalyzed batch are dripped into ahot air column having a temperature of about 375° C. and fall by gravityfor about a distance of 8 ft in the air column. The cured spheres fromthe bottom of the air column are pyrolized in an inert atmosphere at1,000° C. for about 120 minutes. The pyrolized round spheres have a veryuniform size (e.g., monosize distribution), density of about 2.0-2.1g/cc, a diameter of about 400-800 microns, and a crush strength of about(API/ISO) 4-5.5 k psi.

Example 11

A polysilocarb batch has 75% MH, 15% TV, 10% VT and a viscosity of about65 cps. 10 ppm of a platinum and peroxide catalyst mixture is added tothis batch and drops of the catalyzed batch are dripped into a hot aircolumn having a temperature of about 375° C. and fall by gravity forabout a distance of 8 ft in the air column. The cured spheres from thebottom of the air column are pyrolized in an inert atmosphere at 1,000°C. for about 60 minutes. The pyrolized round spheres have a very uniformsize (e.g., monosize distribution), density of about 2.0-2.1 g/cc, adiameter of about 400-800 microns, and a crush strength of about(API/ISO) 4-5.5 k psi.

Example 12

A polysilocarb batch having 70% of the MH and 30% of the VT having amolecular weight of about 500 and about 42% of a submicron and a 325mesh silica are mixed together in a vessel and put in storage for lateruse. The polysilocarb batch has good shelf life and room temperature andthe precursors have not, and do not react with each other. Thepolysilocarb batch has a viscosity of about 300 cps. PsDCs are are madefrom this batch following the methods of Example 1.

Example 13

PsDCs having the following characteristics:

Sizes (mesh) 200, 100, 70, 60, 40, 20, or 10 Specific Gravity (w/in .05g/cc) 1.00 Sphericity/Roundness greater than .95 Clusters (%) 0 ParticleDistribution 95% + within 5 mesh Solubility in 12/3 HCl for 0.5 Hr@<.3.5 150 deg F. Solubility in 10% HCl for 0.5 Hr@ <.2 150 deg F.Settling Rate 2.39 ISO Crush Analysis (>10% fines) >5000

Example 14

PsDCs having the following characteristics.

Sizes (mesh) 200, 100, 70, 60, 40, 20, or 10 Specific Gravity (w/in .05g/cc) 1.10 Sphericity/Roundness greater than .95 Clusters (%) 0 ParticleDistribution 95% + within 5 mesh Solubility in 12/3 HCl for 0.5 Hr@<.3.5 150 deg F. Solubility in 10% HCl for 0.5 Hr@ <.2 150 deg F.Settling Rate 2.89 ISO Crush Analysis (>10% fines) >5000

Example 15

PsDCs having the following characteristics.

Sizes (mesh) 200, 100, 70, 60, 40, 20, or 10 Specific Gravity (w/in .05g/cc) 1.20 Sphericity/Roundness greater than .95 Clusters (%) 0 ParticleDistribution 95% + within 5 mesh Solubility in 12/3 HCl for 0.5 Hr@<.3.5 150 deg F. Solubility in 10% HCl for 0.5 Hr@ <.2 150 deg F.Settling Rate 3.47 ISO Crush Analysis (>10% fines) >5000

Example 16

PsDCs having the following characteristics.

Sizes (mesh) 200, 100, 70, 60, 40, 20, or 10 Specific Gravity (w/in .05g/cc) 1.30 Sphericity/Roundness greater than .95 Clusters (%) 0 ParticleDistribution 95% + within 5 mesh Solubility in 12/3 HCl for 0.5 Hr@<.3.5 150 deg F. Solubility in 10% HCl for 0.5 Hr@ <.2 150 deg F.Settling Rate 4.14 ISO Crush Analysis (>10% fines) >5000

Example 17

PsDCs having the following characteristics.

Sizes (mesh) 200, 100, 70, 60, 40, 20, or 10 Specific Gravity (w/in .05g/cc) 1.40 Sphericity/Roundness greater than .95 Clusters (%) 0 ParticleDistribution 95% + within 5 mesh Solubility in 12/3 HCl for 0.5 Hr@<.3.5 150 deg F. Solubility in 10% HCl for 0.5 Hr@ <.2 150 deg F.Settling Rate 4.90 ISO Crush Analysis (>10% fines) >5000

Example 18

PsDCs having the following characteristics.

Sizes (mesh) 200, 100, 70, 60, 40, 20, or 10 Specific Gravity (w/in .05g/cc) 1.50 Sphericity/Roundness greater than .95 Clusters (%) 0 ParticleDistribution 95% + within 5 mesh Solubility in 12/3 HCl for 0.5 Hr@<.3.5 150 deg F. Solubility in 10% HCl for 0.5 Hr@ <.2 150 deg F.Settling Rate 5.78 ISO Crush Analysis (>10% fines) >5000

Example 19

PsDCs having the following characteristics.

Sizes (mesh) 200, 100, 70, 60, 40, 20, or 10 Specific Gravity (w/in .05g/cc) 1.60 Sphericity/Roundness greater than .95 Clusters (%) 0 ParticleDistribution 95% + within 5 mesh Solubility in 12/3 HCl for 0.5 Hr@<.3.5 150 deg F. Solubility in 10% HCl for 0.5 Hr@ <.2 150 deg F.Settling Rate 6.78 ISO Crush Analysis (>10% fines) >5000

Example 20

PsDCs having the following characteristics.

Sizes (mesh) 200, 100, 70, 60, 40, 20, or 10 Specific Gravity (w/in .05g/cc) 1.70 Sphericity/Roundness greater than .95 Clusters (%) 0 ParticleDistribution 95% + within 5 mesh Solubility in 12/3 HCl for 0.5 Hr@<.3.5 150 deg F. Solubility in 10% HCl for 0.5 Hr@ <.2 150 deg F.Settling Rate 7.92 ISO Crush Analysis (>10% fines) >10,000

Example 21

PsDCs having the following characteristics.

Sizes (mesh) 200, 100, 70, 60, 40, 20, or 10 Specific Gravity (w/in .05g/cc) 1.80 Sphericity/Roundness greater than .95 Clusters (%) 0 ParticleDistribution 95% + within 5 mesh Solubility in 12/3 HCl for 0.5 Hr@<.3.5 150 deg F. Solubility in 10% HCl for 0.5 Hr@ <.2 150 deg F.Settling Rate 9.22 ISO Crush Analysis (>10% fines) >10,000

Example 22

PsDCs having the following characteristics.

Sizes (mesh) 200, 100, 70, 60, 40, 20, or 10 Specific Gravity (w/in .05g/cc) 1.90 Sphericity/Roundness greater than .95 Clusters (%) 0 ParticleDistribution 95% + within 5 mesh Solubility in 12/3 HCl for 0.5 Hr@<.3.5 150 deg F. Solubility in 10% HCl for 0.5 Hr@ <.2 150 deg F.Settling Rate 10.71 ISO Crush Analysis (>10% fines) >10,000

Example 23

PsDCs having the following characteristics.

Sizes (mesh) 200, 100, 70, 60, 40, 20, or 10 Specific Gravity (w/in .05g/cc) 2.00 Sphericity/Roundness greater than .95 Clusters (%) 0 ParticleDistribution 95% + within 5 mesh Solubility in 12/3 HCl for 0.5 Hr@<.3.5 150 deg F. Solubility in 10% HCl for 0.5 Hr@ <.2 150 deg F.Settling Rate 12.40 ISO Crush Analysis (>10% fines) >10,000

Example 24

PsDCs having the following characteristics.

Sizes (mesh) 200, 100, 70, 60, 40, 20, or 10 Specific Gravity (w/in .05g/cc) 2.10 Sphericity/Roundness greater than .95 Clusters (%) 0 ParticleDistribution 95% + within 5 mesh Solubility in 12/3 HCl for 0.5 Hr@<.3.5 150 deg F. Solubility in 10% HCl for 0.5 Hr@ <.2 150 deg F.Settling Rate 14.32 ISO Crush Analysis (>10% fines) >10,000

Example 25

The PsDCs of Example 24 are made having a predetermined mesh size offrom about 8 to about 200, with 95% of the particle size distributionbeing within mesh of the predetermined value. 4,000,000 pounds of thisproppant are mixed with 1 million gallons of slick water fracturingfluid for a fracturing treatment of an unconventional shale formation.

Example 26

The PsDCs of Example 24 are made having a predetermined mesh size offrom about 8 to about 200, with 95% of the particle size distributionbeing within 8 mesh of the predetermined value. 7,000,000 pounds of thisproppant are mixed with 2 million gallons of slick water fracturingfluid for a fracturing treatment of an unconventional shale formation.

Example 27

The PsDCs or Example 24 are made having a predetermined mesh size ofgreater than 200, with 95% of the particle size distribution beingwithin 8 mesh of the predetermined value. 4,000,000 pounds of thisproppant are mixed with 1 million gallons of fracturing fluid for afracturing treatment of a conventional formation.

Example 28

The PsDCs or Example 24 are made having a predetermined mesh size ofgreater than 200, with 95% of the particle size distribution beingwithin 5 mesh of the predetermined value. 7,000,000 pounds of thisproppant are mixed with 2 million gallons of fracturing fluid for afracturing treatment of an unconventional shale formation.

Example 29—Fracturing

Using embodiments of the PsDC of these examples, e.g., Example 2, 35,42, 49, 53, 54, and 55 the following fracture plan is carried out on aformation.

Interval #1

Fracture Half-Length (ft) 263 Propped Half-Length (ft) 204 TotalFracture Height (ft) 307 Total Propped Height (ft) 238 Depth to FractureTop (ft) 5449 Depth to Propped 5518 Fracture Top (ft) Depth to FractureBottom (ft) 5756 Depth to Propped 5756 Fracture Bottom (ft) EquivalentNumber of 1.0 Max. Fracture Width (in) 0.71 Multiple Fracs FractureSlurry Efficiency** 0.74 Avg. Fracture Width (in) 0.39 Avg. Proppant1.51 Concentration (lb/ft²)

Fracture Geometry Summary*—Interval #2

Fracture Half-Length (ft) 244 Propped Half-Length (ft) 193 TotalFracture Height (ft) 308 Total Propped Height (ft) 244 Depth to FractureTop (ft) 5638 Depth to Propped 5702 Fracture Top (ft) Depth to FractureBottom (ft) 5946 Depth to Propped 5946 Fracture Bottom (ft) EquivalentNumber of 1.0 Max. Fracture Width (in) 0.68 Multiple Fracs FractureSlurry Efficiency** 0.74 Avg. Fracture Width (in) 0.41 Avg. Proppant1.52 Concentration (lb/ft²)

Fracture Geometry Summary*—Interval #3

Fracture Half-Length (ft) 252 Propped Half-Length 197 (ft) TotalFracture Height (ft) 305 Total Propped Height 238 (ft) Depth to FractureTop (ft) 5882 Depth to Propped 5949 Fracture Top (ft) Depth to FractureBottom (ft) 6187 Depth to Propped 6186 Fracture Bottom (ft) EquivalentNumber of 1.0 Max. Fracture Width 0.69 Multiple Fracs (in) FractureSlurry Efficiency** 0.73 Avg. Fracture Width 0.39 (in) Avg. Proppant1.52 Concentration (lb/ft²)

Fracture Conductivity Summary*—Interval #1

Avg. Conductivity** 757.0 Avg. Frac Width (Closed 0.104 (mD · ft) onprop) (in) Dimensionless 37.09 Ref. Formation 0.1 Conductivity**Permeability (mD) Proppant Damage 0.50 Undamaged Prop Perm 164207 Factorat Stress (mD) Apparent Damage 0.00 Prop Perm with 82103 Factor*** PropDamage (mD) Total Damage 0.50 Prop Perm with 82103 Factor Total Damage(mD) Effective Propped 196 Proppant Embedment 0.008 Length (ft) (in)

Fracture Conductivity Summary*—Interval #2

Avg. Conductivity** 770.7 Avg. Frac Width (Closed 0.104 (mD · ft) onprop) (in) Dimensionless 39.90 Ref. Formation 0.1 Conductivity**Permeability (mD) Proppant Damage 0.50 Undamaged Prop Perm 164207 Factorat Stress (mD) Apparent Damage 0.00 Prop Perm with Prop 82103 Factor***Damage (mD) Total Damage 0.50 Prop Perm with Total 82103 Factor Damage(mD) Effective Propped 186 Proppant 0.008 Length (ft) Embedment (in)

Fracture Conductivity Summary*—Interval #3

Avg. Conductivity** 749.4 Avg. Frac Width (Closed 0.104 (mD · ft) onprop) (in) Dimensionless 38.05 Ref. Formation 0.1 Conductivity**Permeability (mD) Proppant Damage 0.50 Undamaged Prop Perm 164207 Factorat Stress (mD) Apparent Damage 0.00 Prop Perm with Prop 82103 Factor***Damage (mD) Total Damage 0.50 Prop Perm with Total 82103 Factor Damage(mD) Effective Propped 189 Proppant 0.008 Length (ft) Embedment (in)

Fracture Pressure Summary*—Interval #1

Model Net Pressure** (psi) 727 BH Fracture Closure 5050 Stress (psi)Observed Net Pressure** (psi) 0 Closure Stress 0.898 Gradient (psi/ft)Hydrostatic Head*** (psi) 2670 Avg. Surface Pressure 4007 (psi)Reservoir Pressure (psi) 2635 Max. Surface Pressure 4852 (psi)

Fracture Pressure Summary*—Interval #2

Model Net Pressure** (psi) 707 BH Fracture Closure 5050 Stress (psi)Observed Net Pressure** (psi) 0 Closure Stress 0.867 Gradient (psi/ft)Hydrostatic Head*** (psi) 2670 Avg. Surface Pressure 4007 (psi)Reservoir Pressure (psi) 2635 Max. Surface Pressure 4852 (psi)

Fracture Pressure Summary*—Interval #3

Model Net Pressure** (psi) 694 BH Fracture Closure 5050 Stress (psi)Observed Net Pressure** (psi) 0 Closure Stress 0.834 Gradient (psi/ft)Hydrostatic Head*** (psi) 2670 Avg. Surface Pressure 4007 (psi)Reservoir Pressure (psi) 2635 Max. Surface Pressure 4852 (psi)

Operations Summary*—Interval #1

Total Clean Fluid Pumped 869.7 Total Proppant Pumped 205,800 (bbls)(klbs) Total Slurry Pumped (bbls) 994.1 Total Proppant in Fracture69,500 (klbs) Pad Volume (bbls) 1190.5 Avg. Hydraulic Horsepower 3923(hp) Pad Fraction (% of Slurry 42.9 Max. Hydraulic Horsepower 4751Vol)** (hp) Pad Fraction (% of Clean 49.5 Avg Btm Slurry Rate (bpm) 13.6Vol)** Primary Fluid Type VIKING_D_3500 Primary Proppant Type Example 2Secondary Fluid Type Secondary Proppant Type

Operations Summary*—Interval #2

Total Clean Fluid Pumped 849.0 Total Proppant Pumped 205,800 (bbls)(klbs) Total Slurry Pumped (bbls) 971.6 Total Proppant in Fracture68,300 (klbs) Pad Volume (bbls) 1190.5 Avg. Hydraulic Horsepower 3923(hp) Pad Fraction (% of Slurry 42.9 Max. Hydraulic Horsepower 4751Vol)** (hp) Pad Fraction (% of Clean 49.5 Avg Btm Slurry Rate (bpm) 13.3Vol)** Primary Fluid Type VIKING_D_3500 Primary Proppant Type Example 2Secondary Fluid Type Secondary Proppant Type

Operations Summary*—Interval #3

Total Clean Fluid Pumped 833.2 Total Proppant Pumped 205,800 (bbls)(klbs) Total Slurry Pumped (bbls) 953.5 Total Proppant in Fracture67,000 (klbs) Pad Volume (bbls) 1190.5 Avg. Hydraulic Horsepower 3923(hp) Pad Fraction (% of Slurry 42.9 Max. Hydraulic Horsepower 4751Vol)** (hp) Pad Fraction (% of Clean 49.5 Avg Btm Slurry Rate (bpm) 13.1Vol)** Primary Fluid Type VIKING_D_3500 Primary Proppant Type Example 2Secondary Fluid Type Secondary Proppant Type

Model Calibration Summary

Crack Opening Coefficient 8.50e−01 Width Decoupling Coefficient was1.00e+00 calculated internally Tip Effects Coefficient 1.00e−04 TipRadius Fraction 1.00e−02 Tip Effects Scale Volume (bbls) 100.0 ProppantDrag Effect Exponent 8.0 CLE Outside Payzone 1.00 Multiple fracturessettings start (V/L/O) 1.0/1.0/1.0 Multiple fractures settings end(V/L/O) 1.0/1.0/1.0

Hydraulic Fracture Growth History*—Interval #1

Fracture Avg. Model Fracture Fracture Width at Fracture Net EquivalentEnd of Stage Time Half-Length Height Well Width Pressure Slurry Numberof Stage # Type (mm:ss) (ft) (ft) (in) (in) (psi) Efficiency Multifracs1 Main 29:45 223 220 0.498 0.251 645 0.70 1.0 frac pad 2 Main 31:42 228228 0.506 0.253 646 0.70 1.0 frac slurry 3 Main 33:49 234 236 0.5130.255 646 0.70 1.0 frac slurry 4 Main 41:23 251 260 0.537 0.267 650 0.711.0 frac slurry 5 Main 53:09 257 283 0.593 0.311 678 0.72 1.0 fracslurry 6 Main 69:22 262 303 0.691 0.379 718 0.74 1.0 frac slurry 7 Main72:56 263 307 0.711 0.394 727 0.74 1.0 frac flush

Hydraulic Fracture Growth History*—Interval #2

Fracture Avg. Model Fracture Fracture Width at Fracture Net EquivalentEnd of Stage Time Half-Length Height Well Width Pressure Slurry Numberof Stage # Type (mm:ss) (ft) (ft) (in) (in) (psi) Efficiency Multifracs1 Main 29:45 214 219 0.485 0.254 634 0.69 1.0 frac pad 2 Main 31:42 218226 0.492 0.257 635 0.70 1.0 frac slurry 3 Main 33:49 221 233 0.5050.265 640 0.70 1.0 frac slurry 4 Main 41:23 227 255 0.542 0.291 656 0.711.0 frac slurry 5 Main 53:09 234 285 0.595 0.331 676 0.73 1.0 fracslurry 6 Main 69:22 242 304 0.668 0.400 703 0.74 1.0 frac slurry 7 Main72:56 244 308 0.680 0.413 707 0.74 1.0 frac flush

Hydraulic Fracture Growth History*—Interval #3

Fracture Fracture Avg. Model Half- Fracture Width at Fracture NetEquivalent End of Stage Time Length Height Well Width Pressure SlurryNumber of Stage # Type (mm:ss) (ft) (ft) (in) (in) (psi) EfficiencyMultifracs 1 Main 29:45 211 216 0.474 0.245 613 0.68 1.0 frac pad 2 Main31:42 216 224 0.481 0.247 614 0.68 1.0 frac slurry 3 Main 33:49 221 2310.489 0.250 614 0.68 1.0 frac slurry 4 Main 41:23 238 256 0.516 0.263619 0.69 1.0 frac slurry 5 Main 53:09 246 280 0.572 0.306 645 0.71 1.0frac slurry 6 Main 69:22 251 301 0.669 0.375 685 0.73 1.0 frac slurry 7Main 72:56 252 305 0.689 0.389 694 0.73 1.0 frac flush

Propped Fracture Properties by Distance from the Well at Fracture Centerat Depth of 5603 ft—Interval #1

Frac Fracture Con- Prop System Distance System ductivity Frac SystemConc Prop from Well Width* per Frac** Conductivity*** per Frac Conc****(ft) (in) (mD · ft) (mD · ft) (lb/ft²) (lb/ft²) 20.4 0.617 1106.6 1106.61.55 1.55 40.8 0.611 1573.0 1573.0 2.18 2.18 61.2 0.601 1546.7 1546.72.15 2.15 81.6 0.588 1520.1 1520.1 2.11 2.11 102.0 0.570 1480.5 1480.52.06 2.06 122.5 0.547 1318.5 1318.5 1.85 1.85 142.9 0.519 1224.8 1224.81.73 1.73 163.3 0.485 1039.5 1039.5 1.49 1.49 183.7 0.442 616.9 616.90.93 0.93 204.1 0.390 0.0 0.0 0.00 0.00

Propped Fracture Properties by Distance from the Well at Fracture Centerat Depth of 5792 ft—Interval #2

Frac Fracture Con- Prop System Distance System ductivity Frac SystemConc Prop from Well Width* per Frac** Conductivity*** per Frac Conc****(ft) (in) (mD · ft) (mD · ft) (lb/ft²) (lb/ft²) 19.3 0.628 1566.0 1566.02.17 2.17 38.6 0.622 1580.7 1580.7 2.19 2.19 58.0 0.612 1553.1 1553.12.15 2.15 77.3 0.597 1521.9 1521.9 2.11 2.11 96.6 0.578 1474.4 1474.42.05 2.05 115.9 0.554 1304.3 1304.3 1.83 1.83 135.2 0.524 1222.6 1222.61.73 1.73 154.5 0.487 1051.9 1051.9 1.50 1.50 173.9 0.441 737.4 737.41.09 1.09 193.2 0.384 0.0 0.0 0.00 0.00

Propped Fracture Properties by Distance from the Well at Fracture Centerat Death of 6034 ft—Interval #3

Frac Fracture Con- Prop System Distance System ductivity Frac SystemConc Prop from Well Width* per Frac** Conductivity*** per Frac Conc****(ft) (in) (mD · ft) (mD · ft) (lb/ft²) (lb/ft²) 19.7 0.612 1569.8 1569.82.18 2.18 39.4 0.607 1556.2 1556.2 2.16 2.16 59.1 0.597 1529.8 1529.82.12 2.12 78.8 0.583 1507.9 1507.9 2.10 2.10 98.5 0.565 1465.3 1465.32.04 2.04 118.2 0.543 1302.1 1302.1 1.83 1.83 137.9 0.514 1219.2 1219.21.72 1.72 157.5 0.480 1039.7 1039.7 1.49 1.49 177.2 0.437 678.4 678.41.01 1.01 196.9 0.384 0.0 0.0 0.00 0.00

Treatment Schedule

Elapsed Clean Prop Stage Slurry Stage Time Fluid Volume Conc Prop. RateProppant Stage # Type min:sec Type (gal) (ppg) (klbs) (bpm) TypeWellbore Fluid LINEAR_20_GW- 6050 32 1 Main 29:45 VIKING_D_3500 500000.00 0.0 40.00 frac pad 2 Main 31:42 VIKING_D_3500 3000 1.2 3.6 40.00Example 2 frac slurry 3 Main 33:49 VIKING_D_3500 3000 2.0 2.2 40.00Example 2 frac slurry 4 Main 41:23 VIKING_D_3500 10000 3.6 36.0 40.00Example 2 frac slurry 5 Main 53:09 VIKING_D_3500 15000 4.2 63.0 40.00Example 2 frac slurry 6 Main 69:22 VIKING_D_3500 20000 4.8 96 40.00Example 2 frac slurry 7 Main 72:56 LINEAR_20_GW- 6000 0.00 0.0 40.00frac 32 flush

Proppant and Fluid

Material Quantity Units VIKING_D_3500 2404.8 bbls LINEAR_20_GW-32 142.9bbls Example 2 343.00 klbs

Leakoff Parameters

Reservoir type User Spec Reservoir fluid 3.80e−04 compressibility(1/psi) Filtrate to pore fluid perm. 10.00 Reservoir Viscosity 0.03ratio, Kp/Kl (cp) Reservoir pore pressure 2635 Porosity 0.10 (psi)Initial fracturing pressure 5563 Gas Leakoff 100.00 (psi) Percentage (%)

Reservoir Parameters

Reservoir Temperature (° F.) 176.00 Perforated Interval and Initial FracDepth are for Interval #1 Depth to center of Perfs (ft) 5624 Perforatedinterval (ft) 7 Initial frac depth (ft) 5624

Layer Parameters

Top of Stress Young's Pore Fluid zone Stress Gradient modulus Poisson'sTotal Ct Perm. Layer # (ft) (psi) (psi/ft) (psi) ratio (ft/min½) (mD) 10.0 5238 0.932 2.0e+06 0.25 0.000e+00 0.00e+00 2 5620.0 4692 0.8323.0e+06 0.20 2.208e−03 1.00e−01 3 5660.0 5350 0.932 2.0e+06 0.250.000e+00 0.00e+00 4 5820.0 4859 0.832 3.0e+06 0.20 2.208e−03 1.00e−01 55860.0 5550 0.932 2.0e+06 0.25 0.000e+00 0.00e+00 6 6050.0 5050 0.8323.0e+06 0.20 2.208e−03 1.00e−01 7 6090.0 5676 0.932 2.0e+06 0.250.000e+00 0.00e+00

Lithology Parameters

Fracture Composite Top of zone Toughness Layering Layer # (ft) Lithology(psi · in½) Effect 1 0.0 Shale 2000 1.00 2 5620.0 Sandstone 1000 1.00 35660.0 Shale 2000 1.00 4 5820.0 Sandstone 1000 1.00 5 5860.0 Shale 20001.00 6 6050.0 Sandstone 1000 1.00 7 6090.0 Shale 2000 1.00

Casino Configuration

Length Casing ID Casing OD Weight (ft) Segment Type (in) (in) (lb/ft)Grade 6500 Cemented 4.950 5.500 15.500 K-55 Casing

Perforated Intervals

Interval #1 Interval #2 Interval #3 Top of Perfs - TVD (ft) 5620 58206052 Bot of Perfs - TVD (ft) 5627 5827 6059 Top of Perfs - MD (ft) 56205820 6052 Bot of Perfs - MD (ft) 5627 5827 6059 Perforation Diameter(in) 0.320 0.320 0.320 # of Perforations 7 7 7

Path Summary

Pipe Segment Length MD TVD Dev Ann OD Ann ID ID Type (ft) (ft) (ft)(deg) (in) (in) (in) Casing 6052 6052 6052 0.0 0.000 0.000 4.950

Model Input Parameters

3D Reservoir Data Fracture Model User-Defined Entry Lithology-Based RunFrom Job-Design Data Fracture Vertical Orientation Proppant Proppant RunFracture and Transport Model Convection Wellbore Models Growth afterAllow General Iteration Shut-in Backstress Ignore Heat Transfer IgnoreEffects Acid Fracturing FracproPT Leakoff Model Lumped-Parameter Model(Default) (Default)

Fracture Growth Parameters (3D User-Defined)

Parameter Value Default Crack Opening Coefficient 8.50e−01 8.50e−01 TipEffects Coefficient 1.00e−04 1.00e−04 Channel Flow Coefficient 1.00e+001.00e+00 Tip Radius Fraction 1.00e−02 1.00e−02 Tip Effects Scale Volume(bbls) 100.0 100.0 Fluid Radial Weighting Exponent 0.00e+00 0.00e+00Width Decoupling Coefficient was 1.00e+00 1.00e+00 calculated internally

Proppant Model Parameters

Parameter Value Default Minimum Proppant Concentration (lb/ft²) 0.200.20 Minimum Proppant Diameter (in) 0.0080 0.0080 Minimum DetectableProppant 0.20 0.20 Concentration (ppg) Proppant Drag Effect Exponent 8.08.0 Proppant Radial Weighting Exponent 0.2500 0.2500 Proppant ConvectionCoefficient 10.00 10.00 Proppant Settling Coefficient 1.00 1.00Quadratic Backfill Model ON ON Tip Screen-Out Backfill Coefficient 0.500.50 Stop Model on Screenout ON ON Reset Proppant in Fracture afterClosure ON ON

Low Level Parameters

Parameter Value Default Perm. Contrast: Distance Effect 3.0 1.0 Perm.Contrast: Containment Effect 3.0 1.0 Perm. Contrast: Permeability Level1.00 1.00 Perm. Contrast Model: FracproPT Default YES Fluid <gel> BulkModulus (psi) 3.000e+10 3.000e+10 Proppant Bulk Modulus (psi) 3.000e+063.000e+06 Fluid (gel) Bulk Coefficient of Thermal 3.000e−04 3.000e−04Expansion (1/deg. F.) Effect of Proppant on Length Growth 1.00 1.00Fraction of BRACKET FRAC Proppant that is 0.5 0.5 INVERTA-FRAC by VolumeRemember Position of Proppant Banks after NO NO closure on ProppantAllow Slippage NO NO Reset Fluid Leakoff after Frac Closure NO NOMinimum Volume Limit Value 0.20 0.20 Center Shifting Option: FractureAlways Stays Connected to Perfs X Stages can Move from Perfs afterShut-in X Fracture can Move from Perfs after Shut-in Fracture can Movefrom Perfs at any Time Stage Splitting Volume Threshold (bbls) 200.0200.0 Stage Splitting Leakoff Compensation (bbls) 5.0 5.0

Initial Leakoff and Closure

Parameter Value Default Initial Leakoff Area Multiplier Coefficient1.000 1.000 Initial Leakoff Area from Last Simulation (ft²) 4268.528 n/aClosure Leakoff Area Multiplier Coefficient 0.025 0.025 Default Shut-inModel YES YES Shut-in Tip Weighting Coefficient for Leakoff 1.00 1.00Shut-in Tip Weighting Exponent for Leakoff 1.00 1.00 Minimum Shut-inVolume (bbls) 100.0 100.0 Model Proppant in Flow-back YES YES ModelWall-building Viscosity Effect YES NO

Miscellaneous Growth Parameters

Parameter Value Default Set Minimum Fracture Height NO NO Model VerySmall Fractures NO NO Model Head Effects in Fracture NO NO ModelFracture Center Shifting YES NO Near-Wellbore Friction Exponent 0.500.50

Example 30 Enhanced Hydrocarbon Recovery Using PsDCs

Turning to FIG. 62, there is shown a schematic perspective view of awell 6201 in a portion of a formation 6202. The well 6201 has anessentially horizontal section 6203 that generally follows a reservoirof hydrocarbons in the formation. A perforating operation has beenperformed on the well 6201, leaving perforations, 6204 a, 6204 b, 6204c, 6204 d, 6204 e, 6204 f, 6204 g, 6204 h, 6204 i, 6204 j extending fromthe horizontal section 6203 of well 6201 into the formation 6202. Thereis shown a fracture zone or area, e.g., 6210 a, 6210 b within thereservoir that is typical for prior proppant fracturing, using forexample a sand as the proppant. And, there is shown a fracture zone orarea 6220 a, 6220 b that is obtainable with a PsDC, such as anembodiment of the PsDC proppants of these examples, e.g., Example 2, 35,42, 49, 53, 54, and 55. The PsDC fracture zone 6220 a, 6220 b issubstantially higher (as shown by arrows 6221 a, 6221 b) and longer (asshown by arrows 6222 a, 6222 b each indicating a half-length of thefracture) than the prior art fracture zone 6210 a, 6210 b.

Example 30A

Still using FIG. 62 for illustrative purposes, the low density PsDCs ofExample 2 extend out greater half-lengths 6222 a, and 6222 b away fromthe well 6203 and extend up and down greater heights 6221 a, 6221 b fromthe center line of the perforations, 6204 a-6204 j, providing for asubstantially larger surface area from which the hydrocarbons can flow.These enlarged surface areas may be at least about 20% larger, at leastabout 50% larger, at least about 100% larger, at least about 200% largerand larger still.

This enlarged surface areas 6220 a, 6220 b result in increased initialflows of hydrocarbons by at least about 5%, at least about 10%, at leastabout 20%, at least about 40% and more over the smaller areas 6210 a,6210 b that are obtained with prior proppants.

The PsDC fracture well may also maintain the increased flow, andexperience less degradation of flow or production over time, whencompared to a fractured using prior proppant. Thus, the PsDC fracturedwell may provide natural gas production of at least about 200 Mcf/day,at least about 800 Mcf/day, at least about 1,200 Mcf/day or more for atleast about 12 months, at least about 18 months, at least about 24months or more.

Turning to FIG. 63 there is shown a graph comparing the production overtime of a Marcellus shale gas well using conventional, i.e., priorproppant fracturing 6301, and using PsDC fracturing 6302.

Example 31

A proppant is made from the following precursor batch: 70% MethylHydrogen Fluid; 20% Tetravinyltetramethylcyclotetrasiloxane; and 10%Vinyl Terminated Polydimethylsiloxane (200 cps, ˜9400 Mw, SiSiB® VF6030VINYL TERMINATED POLYDIMETHYL SILOXANE 68083-19-2)

Using a tower system, this batch is formed from a sonic nozzle having aninternal diameter of 0.180 inches into droplets that fall from thenozzle into and through an 18 foot curing tower. The temperature at thetop of the tower is from 200-500° C. the temperature at the bottom ofthe tower is from 200-600° C. There are no discrete temperature zones inthe tower. Airflow up the tower is by convection. The collection pan ismaintained at 110° C. The forming and curing are done in air. Thepreform proppants are removed from the pan and post (hard) cured at 200°C. in air for 3 hours. The hard cured preform proppants are pyrolized at1000° C. in an argon atmosphere for 2 hours. The cure yield is from 99%to 101%. The char yield is 86%.

Example 32

Studies by Coulter & Wells (e.g. SPE JPT, June 1972, pp. 643-650) havedemonstrated that as little as 5% added fines, from prior art proppants,can reduce propped fracture conductivity by 50%. The API (ISO) testclassifies a proppant according to the stress at which <10% fines isgenerated; for example an API (ISO) 7 k proppant would produce <10%fines at 7000 psi. Embodiments of PsDCs, however, exhibit surprising andexceptionally improved conductivities for materials having the same API(ISO) crush strength, when compared to prior art proppants.

Thus, and surprisingly, these embodiments of PsDCs have a substantiallydifferent behavior from prior art proppants. It is believed andtheorized that the PsDCs have a different failure mechanism than priorart proppants.

Thus, it is presently theorized that embodiments of the PsDCs uponfailure exhibit fines that are larger and more jagged than the finesthat are produced upon the failure of prior art proppants. Additionally,it is presently theorized that charge, e.g., the electrostatic charge ofthe PsDCs, could be potentially providing the ability to hold the finestogether, and thus may provide one of may explanations for the enhancedflow and flow back characteristics of embodiments of the PsDC proppants.

Thus, for example, turning to FIG. 64 there is shown a photograph of thefines created at 4 k API (ISO) crush test of the proppants of Example 1;and in FIG. 65 there is shown a photograph of the fines created at 5 kAPI (ISO) crush test of the proppants of Example 1. This can be comparedagainst the fines created from prior art proppants, which are smaller,finer, and more likely to plug, clog, or create a filter cake thatadversely affects conductivity. It is theorized that, for thisembodiment, this different failure mechanism, and different type offines created, explains the increased conductivity values that PsDCsexhibit after failure.

Regardless of the failure mechanism, fluid flow, or hydraulic mechanismstaking place, the PsDCs exhibit surprising and exceptional improvedconductivities over prior art proppants.

Example 33

A polysilocarb formulation has 40% MHF, 40% TV, and 20% VT and has ahydride to vinyl molar ratio of 1.12:1, and may be used as to formstrong ceramic beads, e.g., proppants for use in hydraulicallyfracturing hydrocarbon producing formations.

Example 34

A polysilocarb formulation has 42% MHF, 38% TV, and 20% VT and has ahydride to vinyl molar ratio of 1.26:1, and may be used as to formstrong ceramic beads, e.g., proppants for use in hydraulicallyfracturing hydrocarbon producing formations.

Example 35

A polysilocarb formulation has 46% MHF, 34% TV, and 20% VT and has ahydride to vinyl molar ratio of 1.50:1, and may be used as to formstrong ceramic beads, e.g., proppants for use in hydraulicallyfracturing hydrocarbon producing formations.

Example 36

A polysilocarb formulation has 49% MHF, 31% TV, and 30% VT and has ahydride to vinyl molar ratio of 1.75:1, and may be used as to formstrong ceramic beads, e.g., proppants for use in hydraulicallyfracturing hydrocarbon producing formations.

Example 37

A polysilocarb formulation has 51% MHF, 49% TV, and 0% VT and has ahydride to vinyl molar ratio of 1.26:1, and may be used as to formstrong ceramic beads, e.g., proppants for use in hydraulicallyfracturing hydrocarbon producing formations.

Example 38

A polysilocarb formulation has 55% MHF, 35% TV, and 10% VT and has ahydride to vinyl molar ratio of 1.82:1, and may be used as to formstrong ceramic beads, e.g., proppants for use in hydraulicallyfracturing hydrocarbon producing formations.

Example 39

A polysilocarb formulation has 52% MHF, 28% TV, and 20% VT and has ahydride to vinyl molar ratio of 2.02:1, and may be used as to formstrong ceramic beads, e.g., proppants for use in hydraulicallyfracturing hydrocarbon producing formations.

Example 40

A polysilocarb formulation has 55% MHF, 25% TV, and 20% VT and has ahydride to vinyl molar ratio of 2.36:1, and may be used as to formstrong ceramic beads, e.g., proppants for use in hydraulicallyfracturing hydrocarbon producing formations.

Example 41

A polysilocarb formulation has 65% MHF, 25% TV, and 10% VT and has ahydride to vinyl molar ratio of 2.96:1, and may be used as to formstrong ceramic beads, e.g., proppants for use in hydraulicallyfracturing hydrocarbon producing formations.

Example 42

A polysilocarb formulation has 70% MHF, 20% TV, and 10% VT and has ahydride to vinyl molar ratio of 3:93:1, and may be used as to formstrong ceramic beads, e.g., proppants for use in hydraulicallyfracturing hydrocarbon producing formations.

Example 43

A polysilocarb formulation has 72% MHF, 18% TV, and 10% VT and has ahydride to vinyl molar ratio of 4.45:1, and may be used as to formstrong ceramic beads, e.g., proppants for use in hydraulicallyfracturing hydrocarbon producing formations.

Example 44

A polysilocarb formulation has 75% MHF, 17% TV, and 8% VT and has ahydride to vinyl molar ratio of 4.97:1, and may be used as to formstrong ceramic beads, e.g., proppants for use in hydraulicallyfracturing hydrocarbon producing formations.

Example 45

A polysilocarb formulation has 95% MHF, 5% TV, and 0% VT and has ahydride to vinyl molar ratio of 23.02:1, and may be used as to formstrong ceramic beads, e.g., proppants for use in hydraulicallyfracturing hydrocarbon producing formations.

Example 46

Using the reaction type process a precursor formulation was made usingthe following formulation. The temperature of the reaction wasmaintained at 72° C. for 21 hours. This precursor formulation may beused to make a strong synthetic proppant.

Moles of % of Total % of Reactant/ Moles of Moles Moles Reactant orSolvent Mass Total MW solvent Silane of Si of EtOH Methyltriethoxysilane0.00 0.0% 178.30 — 0.00% — — (FIG. 46) Phenylmethyldiethoxysilane 0.000.0% 210.35 — 0.00% — — (FIG. 47) Dimethyldiethoxysilane 56 7.2% 148.280.38 17.71% 0.38 0.76 (FIG. 51) Methyldiethoxysilane (FIG. 48) 182 23.2%134.25 1.36 63.57% 1.36 2.71 Vinylmethyldiethoxysilane 64 8.2% 160.290.40 18.72% 0.40 0.80 (FIG. 49) Triethoxysilane (FIG. 53) 0.00 0.0%164.27 — 0.00% — — Hexane in hydrolyzer 0.00 0.0% 86.18 — Acetone inhydrolyzer 0.00 0.0% 58.08 — Ethanol in hydrolyzer 400.00 51.1% 46.078.68 Water in hydrolyzer 80.00 10.2% 18.00 4.44 HCl 0.36 0.0% 36.00 0.01Sodium bicarbonate 0.84 0.1% 84.00 0.01

Example 47

Using the reaction type process a precursor formulation was made usingthe following formulation. The temperature of the reaction wasmaintained at 61° C. for 21 hours. This precursor formulation may beused to make a strong synthetic proppant.

Moles of % of Total % of Reactant/ Moles of Moles Moles Reactant orSolvent Mass Total MW solvent Silane of Si of EtOH Phenyltriethoxysilane(FIG. 54) 145.00 18.5% 240.37 0.60 34.58% 0.60 1.81Phenylmethyldiethoxysilane 0.00 0.0% 210.35 — 0.00 — — (FIG. 47)Dimethyldiethoxysilane 0.00 0.0% 148.28 0.57 32.88% 0.57 1.55 (FIG. 51)Methyldiethoxysilane (FIG. 48) 77.00 9.8% 134.25 — 0.00% — —Vinylmethyldiethoxysilane 91.00 11.6% 160.29 0.57 32.54% 0.57 1.14 (FIG.49) Trimethyethoxysilane (FIG. 57) 0.00 0.0% 118.25 — 0.00% — — Acetonein hydrolyzer 395.00 50.3% 58.08 6.80 Ethanol in hydrolyzer 0.00 0.0%46.07 — Water in hydrolyzer 76.00 9.7% 18.00 4.22 HCl 0.36 0.0% 36.000.01 Sodium bicarbonate 0.84 0.1% 84.00 0.01

Example 48

Using the reaction type process a precursor formulation was made usingthe following formulation. The temperature of the reaction wasmaintained at 61° C. for 21 hours. This precursor formulation may beused to make a strong synthetic proppant.

Moles of % of Total % of Reactant/ Moles of Moles Moles Reactant orSolvent Mass Total MW solvent Silane of Si of EtOH ltriethoxysilane(FIG. 54) 0.00 0.00% 240.37 — 0.0% — — Phenylmethyldiethoxysilane 145.0018.4% 210.35 0.69 34.47% 0.69 1.38 (FIG. 47) Dimethyldiethoxysilane 0.000.00% 148.28 — 0.00% — — (FIG.51) Methyldiethoxysilane (FIG. 48) 88.0011.2% 134.25 0.66 32.78% 0.66 1.31 Vinylmethyldiethoxysilane 105.0013.3% 160.29 0.66 32.76% 0.66 1.31 (FIG. 49) Trimethyethoxysilane (FIG.57) 0.00  0.0% 118.25 — 0.00% — — Acetone in hydrolyzer 375.00 47.5%58.08 6.46 Ethanol in hydrolyzer 0.00  0.0% 46.07 — Water in hydrolyzer75.00  9.5% 18.00 4.17 HCl 0.36  0.0% 36.00 0.01 Sodium bicarbonate 0.84 0.1% 84.00 0.01

Example 49

The treatment of pyrolized polysiloxane materials, such as for example,proppants and other volumetric shapes, with silanes, anti-static agentsand combinations of these has the ability to increase, and significantlyincrease the strength of the pyrolized materials.

Thus, treating composition may optionally contain generally used, e.g.,typical, additives such as rheology modifiers, fillers, coalescents suchas glycols and glycol ethers to aid in proppant storage stability,antifoaming agents such as Drew L-139 (commercially available from DrewIndustries, a division of Ashland Chemical), antistatic agents such asEmerstat 6660A (commercially available from Cognis) or Katex 6760 (fromPulcra Chemicals), dust suppression agents, and/or other generally used,e.g., typical, additives. Additives may be present in the coatingscomposition from trace amounts (such as <about 0.1% by weight the totalcomposition) up to about 5.0% by weight of the total composition.

The preferable treating solution contains a silane, Silquest A1100 fromMomentive and has the following chemical formula,H₂NCH₂CH₂CH₂Si(OCH₂CH₃)₃.

To treat proppant the following procedure may be utilized. Wash theProppant in water (current procedure) to remove fines, Wash the Proppantin Silane/Antistat aqueous solution for 5 min (at 25 C). Remove Proppantand save all the excess Silane/Antistat solution for multiple use. Drythe Proppant at 105-110 C for 30 mins-1 hr (preferably it should becompletely dry).

By way of example, 40 mesh proppant having a crush strength of 13,200psi was treated using the above procedure and exhibited crush strengthsthat exceeded 17,600 psi, and more. The fine percentage for these silanetreated proppants was less than 1.7%, and lower.

Example 50 Off Shore Hydrocarbon Recovery

In PsDC hydraulic fracturing treatments of offshore deep water wells isconducted using embodiments of the proppants of these examples, e.g.,Example 2, 16, 17, 18, 21, 23, 35, 42, 49, 53, 54, and 55.

Existing proppants, and in particular generally used higher strengthproppants, that typically have specific gravities of 2.5 and greater(e.g., FIG. 66) are failing to meet the needs of the deep water offshorehydrocarbon E&P. Such proppants increase the weight of the fracturingfluid to such an extent that pumps have great difficulty, and in manycases cannot reverse the flow of the fracturing fluid and pump the fluidfrom the well, if need be, during a fracturing treatment. This inabilityto reverse, back off, or have full control of the fracturing fluid, canresult delays, cost increases, and in some cases in severe and costlydamage to the well. For example, this problem can arise in water depthsof 5,000 feet, and increases as the water depth, and thus the length ofthe riser, and column of fracturing fluid in the riser increases. Thus,the problem becomes more pronounced in water depths of 7,000 feet andgreater, 8,000 feet and greater, and 10,000 feet and greater. Theproblem is further complicated by the MD of the wells, which furtherincreases the total weight of the column of fracturing fluid that mustbe backed off, reverse flowed, or otherwise controlled. Thus, MDs of10,000 feet and greater, 15,000 feet and greater, and 20,000 feet andgreater provide significant addition weight, especially when combinedwith a 5,000 foot and greater column of fracture fluid in the riser.

The low specific gravity, e.g., less than 2.5, and more preferably lessthan 2.0, and low specific gravity to high strength ratio, provided bythe synthetic proppants of the present inventions, greatly reduces theweight of the column of fracturing fluid providing the ability to backoff, circulate, reverse flow, and otherwise control the movement of thefracturing fluid, and thus solves this developing, significant andpotentially severe problem with prior proppants, as E&P activities moveinto deeper and deeper waters.

Example 50a

Turning to FIG. 70 there is shown a perspective view of an off shorewell. An off shore rig 7000, e.g., a dynamically positioned drill ship,has fracturing equipment 7002. The drill ship 7000 is located on thesurface 7003 of a body of water 7004. A riser 7006 extends down from thedrill ship 7000 to a BOP 7008 located on the sea floor 7005. Theborehole 7101 extends below the sea floor 7005 to a fracture area 7012.The MD for the borehole from the sea floor to the fracture area 7012 is10,000 feet (unless stated otherwise, in off shore wells MD is from thesea floor as the reference point). The sea floor is at a depth of about8,000 feet and the riser has a length of about that same distance. Theproppant of Example 54 is used to perform a hydraulic fracturingtreatment on the fracturing area 7012.

Example 50b

Turning to FIG. 71 there is shown a cross sectional view of an off shorewell. An off shore rig 7100, e.g., a dynamically positionedsemi-submersible, has a vessel 7101 having fracturing equipment. The rig7100 is located on the surface 7103 of a body of water 7104. A riser7106 extends down from the drill ship 7100 to a BOP 7108 located on thesea floor 7105. The borehole extends below the sea floor 7105 to afracture area 7112. The borehole has casings 7109, 7110. A pipe 7107 fortransporting the fracturing fluid to the fracturing area 7112 extendsfrom the rig 7100 to the fracture area 7112. Perforations, e.g., 7113are present in the fracture area 7112. An annulus 7111 is located aroundthe pipe 7107 and extends from the fracture area 7112 to the drill ship7100 (during different stages, points of the fracturing treatment isunderstood that packers may be engaged, and disengaged, at strategicpoints in the annulus). The MD at the fracture area 7112 is about 15,000feet. The sea floor is at a depth of about 9,000 feet and the riser hasa length of about that same distance. The proppant of Example 55 is usedto perform a hydraulic fracturing treatment on the fracturing area 7012.

Example 51

In a PsDC hydraulic fracturing treatment the PsDC proppants are added ina controlled manner, and at a controlled lbs/gal, using volumetricmetering devices.

Example 52

In a PsDC hydraulic fracturing treatment the PsDC proppants are addedusing volumetric metering devices. The proppant is metered into the highpressure line, in a controlled manner. In this manner the pumps are notrequired to pump fracturing fluid containing proppant.

Example 53

A PsDC proppant of the type of Example 42 has the following features:high in strength resulting in less crushing, optimizing conductivity andminimizing fines generation; lower specific gravity enabling theproppant to travel further into the formation, creating longer proppedfracture half-lengths and more propped surface area, resulting ingreater access to reserves in place generating higher initial production(IP) and increased estimated ultimate recovery (EUR); performs well attemperatures to >2,000° F. (1,100° C.), enabling usage in virtually allO&G reservoirs; is round and has a uniform mesh distribution, maximizingconductivity and increasing the free flow of formation liquids; lowerstotal well costs per unit of production; not harmful to the environmentand could reduce the number of wells producers must drill given itsability to access more of the reserves in place.

The proppant has a sieve analysis (% retained) of +35 Mesh/420microns—0.1%; −35+40 mesh/354 microns—72.8%; −40+45 mesh/297microns—27.1%; −45 mesh/250 microns—0%. The proppant has a roundness ofabout 1.0, a sphericity of about 1.0, a bulk density of 75.15 (lbs/ft³)1.20 (g/cc), a specific gravity of 1.98, an absolute volume of 0.61(gal/lb), a solubility in 12/3 HCl/HF Acid (% weight loss) 5.7, APIcrush test, % of fines generated @ 15,000 psi 0.3.

The proppant has the long term conductivity data of Tables 4a and 4b

TABLE 4a Closure Stress (psi) md-ft (millidarcy- 2 lbs/ft² 40 mesh feet)@ 250° F. 2,000 2,743 4,000 2,510 6,000 2,228 8,000 1,697 10,000 1,60712,000 1,544 14,000 1,366 15,000 1,228

TABLE 4b Closure stress (psi) 2 lbs/ft3 40 mesh Darcies @ 250° F. 2,000133 4,000 124 6,000 113 8,000 86 10,000 84 12,000 82 14,000 74 15,000 67

Example 54

An embodiment of the proppant of Example 39 has a bulk density of 1.17g/cc, a specific gravity of 1.93, a particle size distribution of 0.1%at 35 mesh, 75.2% at 40 mesh, 24.6% at 45 mesh, and 0.1% at 50 mesh, andan ISO Crush Analysis (% fines) 4 lb/ft² @ 15,000 psi of 0.6. The sampleexhibits exceptional long term conductivity performance data as shown inTable 5.

TABLE 5 Pack Height (Test cell Time Total test plate Stress (hrs) @ timeConductivity Permeability separation) (psi) stress (hrs) (md-ft) (Darcy)(in)  1,000 24  24 2263 111 0.246  2,000 50  74 1977  99 0.240  4,000 50124 1841  93 0.237  6,000 50 174 1940 100 0.233  8,000 50 224 1769  930.229 10,000 50 274 1762  94 0.226 12,000 50 324 1638  89 0.221 14,00050 374 1381  77 0.215 15,000 50 424 1187  68 0.209

Example 55

An embodiment of the proppant of Example 35 has a bulk density of 1.24g/cc, a specific gravity of 1.95, a particle size distribution of 0.1%at 35 mesh, 91.6% at 40 mesh, 8.2% at 45 mesh, and 0.1% at 50 mesh, andan ISO Crush Analysis (% fines) 4 lb/ft² @ 15,000 psi of 0.4. A 400×photograph of these proppants is shown in FIG. 69. The sample exhibitsexceptional long term conductivity performance data as shown in Table 6.

TABLE 6 Pack Height (Test cell Time Total plate Stress (hrs) @ test timeConductivity Permeability separation) (psi) stress (hrs) (md-ft) (Darcy)(in)  1,000 24 24 2777 127 0.262  2,000 50 74 2344 110 0.256  4,000 50124 2051 98 0.251  6,000 50 174 1912 93 0.247  8,000 50 224 1681 820.245 10,000 50 274 1916 94 0.244 12,000 50 324 1717 86 0.240 14,000 50374 1461 75 0.233 15,000 50 424 1247 65 0.229

Example 56

Embodiments of a PsDC formulations of Examples 35, 39 and 42 are formedinto pucks. The pucks are cures and pyrolized to a ceramic. The ceramicpucks are broken apart, into small particles. The particles are sievedif need be, to have the majority of all particles smaller than 100 mesh.These particles are not spherical, are irregular and varied in shape,and have planar surfaces. These particles are PsDC proppants

Example 57

Embodiments of a PsDC formulations of Examples 35, 39 and 42 are formedinto pucks. The pucks are cures and pyrolized to a ceramic. The ceramicpucks are broken apart, into small particles. The particles are sievedif need be, to have the majority of all particles smaller than 200 mesh.These particles are not spherical, are irregular and varied in shape,and have planar surfaces. These particles are PsDC proppants

Example 58

Embodiments of the proppants of these examples, e.g., Examples 56, 57,59 and 60, are used in a hydraulic fracture treatment of anunconventional shale well. The fractures are propped with a monolayer orpartial monolayer distribution of proppant. It is theorized that aself-bridging diverting phenomena takes place in situ. Prior proppants,now generally in use, do not get very far from the well bore due tosettling because of their density. Embodiments of proppants of thepresent inventions can accomplish this due to, among other things, theirsize and lower density.

Example 59

Embodiments of a PsDC formulations of Examples 35, 39 and 42 are formedinto small spheres using emulsion polymerization techniques. Theprecursor formulation is emulsified using water, alcohol, glycol, or anypolar liquid having a low partition coefficient, and in which theprecursor formulation is not soluble, as the emulsifier. Once formed theemulsion is broken and the small sphere are cured and pyrolized intoPsDC proppants. The spheres are smaller than 100 mesh.

Example 60

Embodiments of a PsDC formulations are formed into small spheres usingemulsion polymerization techniques. The precursor formulation isemulsified using water, alcohol, glycol, or any polar liquid having alow partition coefficient, and in which the precursor formulation is notsoluble, as the emulsifier. Once formed the emulsion is broken and thesmall sphere are cured and pyrolized into PsDC proppants. The spheresare smaller than 100 mesh. In other embodiments the spheres are smallerthan 150 mesh. In other embodiments the spheres are smaller than 200mesh, and smaller.

Example 61

A jack-up off shore rig has fracturing equipment operationallyassociated with it. The rig is located above the surface of a body ofwater having a depth of 200 feet. A riser extends down from the rig to aBOP on the sea floor, and has a length of about 200 feet. A boreholeextends below the sea floor into the earth to a fracture area at a MD ofabout 8,000 feet. The proppant of Example 55 is used to perform ahydraulic fracturing treatment on the fracturing area.

It is noted that there is no requirement to provide or address thetheory underlying the novel and groundbreaking conductivities,performance or other beneficial features and properties that are thesubject of, or associated with, embodiments of the present inventions.Nevertheless, various theories are provided in this specification tofurther advance the art in this important area, and in particular in theimportant area of hydrocarbon exploration and production. These theoriesput forth in this specification, and unless expressly stated otherwise,in no way limit, restrict or narrow the scope of protection to beafforded the claimed inventions. These theories many not be required orpracticed to utilize the present inventions. It is further understoodthat the present inventions may lead to new, and heretofore unknowntheories to explain the conductivities, fractures, drainages, resourceproduction, and function-features of embodiments of the methods,articles, materials, devices and system of the present inventions; andsuch later developed theories shall not limit the scope of protectionafforded the present inventions.

The various embodiments of formulations, batches, devices, systems,proppants, PsDCs, methods, hydraulic fracture treatments, hydrocarbonrecovery, activities and operations set forth in this specification maybe used for various oil field operations, other mineral and resourcerecovery fields, as well as other activities and in other fields.Additionally, these embodiments, for example, may be used with: oilfield systems, operations or activities that may be developed in thefuture; and with existing oil field systems, operations or activitieswhich may be modified, in-part, based on the teachings of thisspecification. Further, the various embodiments set forth in thisspecification may be used with each other in different and variouscombinations. Thus, for example, the configurations provided in thevarious embodiments of this specification may be used with each other;and the scope of protection afforded the present inventions should notbe limited to a particular embodiment, configuration or arrangement thatis set forth in a particular embodiment, example, or in an embodiment ina particular Figure.

Although this specification focuses on proppants, it should beunderstood that the formulations, material systems, small volumetricshapes, and methods of making them, taught and disclosed herein, mayhave applications and uses for many other activities in addition tohydraulic fracturing, for example, as pigments and additives.

The invention may be embodied in other forms than those specificallydisclosed herein without departing from its spirit or essentialcharacteristics. The described embodiments are to be considered in allrespects only as illustrative and not restrictive.

What is claimed:
 1. A method of hydraulically fracturing a well, themethod comprising: a. preparing at least about 100,000 gallons of ahydraulic fracturing fluid, the hydraulic fracturing fluid comprising apolysiloxane derived ceramic proppant made by the process of firstcuring a polysiloxane precursor batch to form a cured bead andpyrolizing the cured bead to form the polysiloxane derived ceramicproppant; b. pumping at least about 100,000 gallons of hydraulicfracturing fluid into a borehole in a formation, and out of the boreholeinto the formation; whereby fractures are created in the formation; and,c. leaving at least some of the proppant in the fractures.
 2. The methodof claim 1, wherein the fracturing fluid has at least about 2 lbs pergallon of proppant.
 3. The method of claim 1, wherein the fracturingfluid has at least 3 lbs per gallon of proppant.
 4. The method of claim1, wherein the fracturing fluid has at least 4 lbs per gallon ofproppant.
 5. The method of claim 1, wherein the proppants have aparticle size distribution of at least about 95% of the proppants beingwithin about a 10 mesh range.
 6. The method of claim 1, wherein theproppants have a specific gravity of less 1.9.
 7. The method of claim 1,wherein the proppants have a bulk density of less about 1.3 g/cc.
 8. Themethod of claim 1, wherein the formation is a shale formation.
 9. Themethod of claim 8, wherein the shale formation is Eagleford shale. 10.The method of claim 8, wherein the shale formation is Barnett shale. 11.The method of claim 8, wherein the shale formation is Bakken shale. 12.The method of claim 8, wherein the shale formation is Utica shale.
 13. Amethod of hydraulically fracturing a well, the method comprising: a.preparing at least about 100,000 gallons of a hydraulic fracturingfluid, the hydraulic fracturing fluid comprising a synthetic proppant;b. the proppant having an apparent specific gravity of less than about 2and a crush test of less than about 1% fines generated at 10,000 psi.;c. pumping at least about 100,000 gallons of hydraulic fracturing fluidinto a borehole in a formation, and out of the borehole into theformation; whereby fractures are created in the formation; and, d.leaving at least some of the proppant in the fractures.
 14. The proppantof claim 13, wherein the proppant consists essentially of silicon,carbon and oxygen.
 15. The method of claim 13, wherein the fracturingfluid has at least about 2 lbs per gallon of proppant.
 16. The method ofclaim 13, wherein the fracturing fluid has at least 3 lbs per gallon ofproppant.
 17. The method of claim 13, wherein the fracturing fluid hasat least 4 lbs per gallon of proppant.
 18. The method of claim 14,wherein the fracturing fluid has at least about 2 lbs per gallon ofproppant.
 19. The method of claim 14, wherein the fracturing fluid hasat least 3 lbs per gallon of proppant.
 20. The method of claim 14,wherein the fracturing fluid has at least 4 lbs per gallon of proppant.21. The proppant of claim 15, wherein the proppant consists essentiallyof silicon, carbon and oxygen.
 22. The method of claim 14, wherein thefracturing fluid has at least about 2 lbs per gallon of proppant. 23.The method of claim 15, wherein the fracturing fluid has at least about2 lbs per gallon of proppant.
 24. The method f claim 13, wherein theformation is a shale formation.
 25. The method of claim 24, wherein theshale formation is Eagleford shale.
 26. The method of claim 24, whereinthe shale formation is Barnett shale.
 27. The method of claim 24,wherein the shale formation is Bakken shale.
 28. The method of claim 24,wherein the shale formation is Utica shale.
 29. The method of claim 13,wherein the fracturing fluid has at least about 10 lbs per gallon ofproppant.
 30. The method of claim 13, wherein the fracturing fluid hasat least 10 lbs per gallon of proppant.
 31. The method of claim 13,wherein the fracturing fluid has at least 10 lbs per gallon of proppant.32. A method of hydraulically fracturing a well, the method comprising:a. preparing at least about 100,000 gallons of a hydraulic fracturingfluid, the hydraulic fracturing fluid comprising a synthetic proppant;b. the proppant having an apparent specific gravity of less than about2.0 and a crush test of less than about 1% fines generated at 15,000psi., c. pumping at least about 100,000 gallons of hydraulic fracturingfluid into a borehole in a formation, and out of the borehole into theformation; whereby fractures are created in the formation; and, d.leaving at least some of the proppant in the fractures.